U.S. patent application number 16/890071 was filed with the patent office on 2021-10-14 for electrochromic compounds and devices.
The applicant listed for this patent is Gentex Corporation. Invention is credited to Zachary B. Erno, Punam Giri.
Application Number | 20210318584 16/890071 |
Document ID | / |
Family ID | 1000005866191 |
Filed Date | 2021-10-14 |
United States Patent
Application |
20210318584 |
Kind Code |
A9 |
Erno; Zachary B. ; et
al. |
October 14, 2021 |
ELECTROCHROMIC COMPOUNDS AND DEVICES
Abstract
An electro-optic element includes a first substrate defining
first and second surfaces and a second substrate defining third and
fourth surfaces. A first electrically conductive layer is disposed
on the second surface and a second electrically conductive layer is
disposed on the third surface. An electrochromic medium is disposed
in a cavity between the first and second substrates, the
electrochromic medium including an anodic component and a cathodic
component. At least the anodic component is configured to
reversibly attenuate transmittance of light having a wavelength
within a predetermined wavelength range when in an
electrochemically activated state. The anodic component includes a
substituted ketal phenazine compound.
Inventors: |
Erno; Zachary B.;
(Hudsonville, MI) ; Giri; Punam; (Holland,
MI) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Gentex Corporation |
Zeeland |
MI |
US |
|
|
Prior
Publication: |
|
Document Identifier |
Publication Date |
|
US 20200379309 A1 |
December 3, 2020 |
|
|
Family ID: |
1000005866191 |
Appl. No.: |
16/890071 |
Filed: |
June 2, 2020 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
62856321 |
Jun 3, 2019 |
|
|
|
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C07D 405/14 20130101;
G02F 2001/15145 20190101; G02F 1/1516 20190101 |
International
Class: |
G02F 1/1516 20060101
G02F001/1516; C07D 405/14 20060101 C07D405/14 |
Claims
1. An electro-optic element, comprising: a first substrate defining
first and second surfaces, wherein a first electrically conductive
layer is disposed on the second surface; a second substrate
defining third and fourth surfaces, wherein a second electrically
conductive layer is disposed on the third surface; and an
electrochromic medium disposed in a cavity between the first and
second substrates, the electrochromic medium including an anodic
component and a cathodic component; wherein at least the anodic
component is configured to reversibly attenuate transmittance of
light having a wavelength within a predetermined wavelength range
when in an electrochemically activated state; and wherein the
anodic component comprises a compound of Formula (I): ##STR00010##
wherein R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.6, R.sub.7,
R.sub.8, R.sub.9, R.sub.11, and R.sub.12 are individually a
hydrogen, alkyl, substituted alkyl, straight chain alkyl, branched
alkyl, or cycloalkyl and R.sub.5 and R.sub.10 are individually an
alkyl, substituted alkyl, straight chain alkyl, branched alkyl, or
cycloalkyl.
2. The electro-optic element of claim 1, wherein one of: R.sub.5
and R.sub.10; R.sub.11 and R.sub.12; or R.sub.5, R.sub.10,
R.sub.11, and R.sub.12, individually comprise an alkyl, substituted
alkyl, straight chain alkyl, branched alkyl, or cycloalkyl
substituted with at least one polymerizable functional group.
3. The electro-optic element of claim 2, wherein the polymerizable
functional group comprises at least one group selected from a vinyl
group, acrylate group, methacrylate group, vinyl ether group,
hydroxyl group, isocyanate group, oxetane group, amine group, and
epoxy group.
4. The electro-optic element of claim 1, wherein at least one of
R.sub.2, R.sub.5, R.sub.7, and R.sub.10 are free of beta
hydrogens.
5. The electro-optic element of claim 4, wherein at least one of
R.sub.2, R.sub.5, R.sub.7, and R.sub.10 comprises one of a
neopentyl group and tertiary alkyl.
6. The electro-optic element of claim 1, wherein the anodic
component comprises at least one material selected from
4-(2-tert-butyl-2-{7-[2-tert-butyl-4-(4-hydroxylbutyl)-1,3-dioxolan-2-yl}-
-5,10-bis(2,2-dimethylpropyl)
phenazine-2-yl)-1,3-dioxolan-4-yl}butane-1-ol (Compound (I)) and
4-(2-tert-butyl-2-{7-[2-tert-butyl-4-(4-hydroxymethyl)-1,3-dioxolan-2-yl]-
-5,10-bis(2,2-dimethylpropyl) phenazine-2-yl}-1,3-dioxolan-4-yl)
methanol (Compound (II)): ##STR00011##
7. The electro-optic element of claim 1, wherein the anodic
component further comprises at least one additional anodic
compound, and wherein: the compound of Formula (I) comprises a
maximum absorption in a wavelength range of 400 nm to 550 nm, when
in an electrochemically activated state; and the at least one
additional anodic compound comprises a maximum absorption in a
wavelength range of 400 nm to 550 nm, when in an electrochemically
activated state, and wherein the maximum absorption of the compound
of Formula (I) is within .+-.50 nm of the maximum absorption of the
at least one additional anodic compound, when the compound of
Formula (I) and the at least one additional anodic compound are in
an electrochemically activated state.
8. The electro-optic element of claim 7, wherein the compound of
Formula (I) comprises an oxidation potential and the at least one
additional anodic compound comprises an oxidation potential, and
wherein: the oxidation potential of the compound of Formula (I) is
within .+-.60 millivolts of the oxidation potential of the at least
one additional anodic compound.
9. The electro-optic element of claim 7, wherein the at least one
additional anodic compound comprises at least one material selected
from metallocenes, 5,10-dihydrophenazines, phenothiazines,
phenoxazines, carbazoles, triphenodithiazines, triphendioxazines,
ferrocene, substituted ferrocenes, substituted ferrocenyl salts,
phenazine, substituted phenazines, phenothiazine, substituted
phenothiazines, including substituted dithiazines, thianthrene and
substituted thianthrenes, di-tert-butyl-diethylferrocene,
5,10-dimethyl-5,10-dihydrophenazine (DMP),
3,7,10-trimethylphenothiazine, 2,3,7,8-tetramethoxy-thianthrene,
10-methylphenothiazine, tetramethylphenazine (TMP),
bis(butyltriethylammonium)-para-methoxytriphenodithiazine (TPDT),
3,10-dimethoxy-7,14-(triethylammoniumbutyl)-triphenodithazinebis(tetraflu-
oroborate), and combinations thereof.
10. The electro-optic element of claim 1, wherein the cathodic
component comprises at least one material selected from a viologen,
low-dimerizing viologen, non-dimerizing viologen, substituted
viologen, di-acrylate viologen, cathodic di-vinyl viologen,
cathodic di-vinyl ether viologen, cathodic di-epoxy viologen,
cathodic di-oxetane viologen, cathodic di-hydroxy viologen, and
combinations thereof.
11. The electro-optic element of claim 1, wherein the anodic
component is one of dissolved in a solvent, incorporated into a
gel, or incorporated into a polymeric film.
12. A medium for an electro-optic element, comprising: an anodic
component configured to reversibly attenuate transmittance of light
having a wavelength within a predetermined wavelength range when in
an electrochemically activated state, and wherein the anodic
component comprises a compound of Formula (I): ##STR00012## wherein
R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.6, R.sub.7, R.sub.8,
R.sub.9, R.sub.11, and R.sub.12 are individually a hydrogen, alkyl,
substituted alkyl, straight chain alkyl, branched alkyl, or
cycloalkyl and R.sub.5 and R.sub.10 are individually an alkyl,
substituted alkyl, straight chain alkyl, branched alkyl, or
cycloalkyl.
13. The medium of claim 12, wherein one of: R.sub.5 and R.sub.10;
R.sub.11 and R.sub.12; or R.sub.5, R.sub.10, R.sub.11, and
R.sub.12, individually comprise an alkyl, substituted alkyl,
straight chain alkyl, branched alkyl, or cycloalkyl substituted
with at least one polymerizable functional group.
14. The medium of claim 13, wherein the at least one polymerizable
functional group comprises at least one group selected from a vinyl
group, acrylate group, methacrylate group, vinyl ether group,
hydroxyl group, isocyanate group, oxetane group, amine group, and
epoxy group.
15. The medium of claim 12, wherein at least one of R.sub.2,
R.sub.5, R.sub.7, and R.sub.10 are free of beta hydrogens.
16. The medium of claim 15, wherein at least one of R.sub.2,
R.sub.5, R.sub.7, and R.sub.10 comprises one of a neopentyl group
and tertiary alkyl.
17. The medium of claim 12, wherein the anodic component comprises
at least one material selected from
4-(2-tert-butyl-2-{7-[2-tert-butyl-4-(4-hydroxylbutyl)-1,3-dioxolan-2-yl}-
-5,10-bis(2,2-dimethylpropyl)
phenazine-2-yl)-1,3-dioxolan-4-yl}butane-1-ol (Compound (I)) and
4-(2-tert-butyl-2-{7-[2-tert-butyl-4-(4-hydroxymethyl)-1,3-dioxolan-2-yl]-
-5,10-bis(2,2-dimethylpropyl) phenazine-2-yl}-1,3-dioxolan-4-yl)
methanol (Compound (II)): ##STR00013##
18. The medium of claim 12, wherein the anodic component further
comprises at least one additional anodic compound, and wherein: the
compound of Formula (I) comprises a maximum absorption in a
wavelength range of 400 nm to 550 nm, when in an electrochemically
activated state; and the at least one additional anodic compound
comprises a maximum absorption in a wavelength range of 400 nm to
550 nm, when in an electrochemically activated state; wherein the
maximum absorption of the compound of Formula (I) is within .+-.50
nm of the maximum absorption of the at least one additional anodic
compound, when the compound of Formula (I) and the additional
anodic compound are in an electrochemically activated state.
19. The medium of claim 18, wherein the compound of Formula (I)
comprises an oxidation potential and the at least one additional
anodic compound comprises an oxidation potential, and wherein: the
oxidation potential of the compound of Formula (I) is within .+-.60
millivolts of the oxidation potential of the at least one
additional anodic compound.
20. The medium of claim 19, wherein the at least one additional
anodic compound comprises at least one material selected from
metallocenes, 5,10-dihydrophenazines, phenothiazines, phenoxazines,
carbazoles, triphenodithiazines, triphendioxazines, ferrocene,
substituted ferrocenes, substituted ferrocenyl salts, phenazine,
substituted phenazines, phenothiazine, substituted phenothiazines,
including substituted dithiazines, thianthrene and substituted
thianthrenes, di-tert-butyl-diethylferrocene,
5,10-dimethyl-5,10-dihydrophenazine (DMP),
3,7,10-trimethylphenothiazine, 2,3,7,8-tetramethoxy-thianthrene,
10-methylphenothiazine, tetramethylphenazine (TMP),
bis(butyltriethylammonium)-para-methoxytriphenodithiazine (TPDT),
3,10-dimethoxy-7,14-(triethylammoniumbutyl)-triphenodithazinebis(tetraflu-
oroborate), and combinations thereof.
Description
CROSS-REFERENCE TO RELATED APPLICATION
[0001] This application claims priority to and the benefit under 35
U.S.C. .sctn. 119(e) of U.S. Provisional Application No.
62/856,321, filed on Jun. 3, 2019, entitled ELECTROCHROMIC
COMPOUNDS AND DEVICES, the disclosure of which is hereby
incorporated herein by reference in its entirety.
FIELD OF THE DISCLOSURE
[0002] The present disclosure generally relates to electrochromic
compounds for electro-optic elements and mediums, and more
particularly to substituted ketal phenazines suitable for use as an
electrochromic component.
SUMMARY OF THE DISCLOSURE
[0003] According to one aspect of the present disclosure, an
electro-optic element includes a first substrate defining first and
second surfaces, wherein a first electrically conductive layer is
disposed on the second surface, and a second substrate defining
third and fourth surfaces, wherein a second electrically conductive
layer is disposed on the third surface. An electrochromic medium is
disposed in a cavity between the first and second substrates, the
electrochromic medium including an anodic component and a cathodic
component. At least the anodic component is configured to
reversibly attenuate transmittance of light having a wavelength
within a predetermined wavelength range when in an
electrochemically activated state. The anodic component comprises a
compound of Formula (I):
##STR00001##
[0004] wherein R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.6,
R.sub.7, R.sub.8, R.sub.9, R.sub.11, and R.sub.12 are individually
a hydrogen, an alkyl, a substituted alkyl, a straight chain alkyl,
a branched alkyl, or a cycloalkyl and R.sub.5 and R.sub.10 are
individually an alkyl, a substituted alkyl, a straight chain alkyl,
a branched alkyl, or a cycloalkyl.
[0005] According to an aspect of the present disclosure, a medium
for an electro-optic element includes an anodic component
configured to reversibly attenuate transmittance of light having a
wavelength within a predetermined wavelength range when in an
electrochemically activated state, wherein the anodic component
comprises a compound of Formula (I):
##STR00002##
[0006] wherein R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.6,
R.sub.7, R.sub.8, R.sub.9, R.sub.11, and R.sub.12 are individually
a hydrogen, an alkyl, a substituted alkyl, a straight chain alkyl,
a branched alkyl, or a cycloalkyl and R.sub.5 and R.sub.10 are
individually an alkyl, a substituted alkyl, a straight chain alkyl,
a branched alkyl, or a cycloalkyl.
[0007] These and other features, advantages, and objects of the
present disclosure will be further understood and appreciated by
those skilled in the art by reference to the following
specification, claims, and appended drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0008] In the drawings:
[0009] FIG. 1 is a cross-sectional schematic view of an
electrochromic device including an electro-optic element, according
to aspects of the present disclosure;
[0010] FIG. 2A is a cross-sectional schematic view of an
electro-optic element, according to an aspect of the present
disclosure;
[0011] FIG. 2B is a cross-sectional schematic view of an
electro-optic element, according to an aspect of the present
disclosure;
[0012] FIG. 2C is a cross-sectional schematic view of an
electro-optic element, according to an aspect of the present
disclosure;
[0013] FIG. 2D is a cross-sectional schematic view of an
electro-optic element, according to an aspect of the present
disclosure;
[0014] FIG. 2E is a cross-sectional schematic view of an
electro-optic element, according to an aspect of the present
disclosure;
[0015] FIG. 3A illustrates the chemical structure of an exemplary
electrochromic compound, according to an aspect of the present
disclosure;
[0016] FIG. 3B illustrates the chemical structure of an exemplary
electrochromic compound, according to an aspect of the present
disclosure;
[0017] FIG. 4 is a flow chart depicting a synthetic scheme for
synthesizing an exemplary electrochromic compound, according to an
aspect of the present disclosure;
[0018] FIG. 5 is a plot of absorbance as a function of wavelength
for an exemplary electrochromic compound according to an aspect of
the present disclosure and a comparative electrochromic
compound;
[0019] FIG. 6 is a plot of absorbance as a function of wavelength
for an exemplary electrochromic device including an electrochromic
compound according to an aspect of the present disclosure and a
comparative electrochromic medium; and
[0020] FIG. 7 is a plot of CIE LAB color space color values a* and
b* of an electrochromic device as an applied potential is increased
from 0 volts to 0.8 volts for a first and second exemplary
electrochromic medium (Ex. 3A and Ex. 3B, respectively) according
to an aspect of the present disclosure and a comparative
electrochromic medium (Comp. Ex. 3A).
DETAILED DESCRIPTION
[0021] The present illustrated embodiments reside primarily in
combinations of materials, method steps, and apparatus components
relating to an electrochromic medium and electro-optic element that
includes an anodic component configured to reversibly attenuate
transmittance of light having a wavelength within a predetermined
wavelength range when in an electrochemically activated state, the
anodic component being a substituted ketal phenazine compound
according to Formula (I), as discussed below. Accordingly, the
apparatus components and method steps have been represented, where
appropriate, by conventional symbols in the drawings, showing only
those specific details that are pertinent to understanding the
embodiments of the present disclosure so as not to obscure the
disclosure with details that will be readily apparent to those of
ordinary skill in the art having the benefit of the description
herein. Further, like numerals in the description and drawings
represent like elements.
[0022] As used herein, the term "and/or," when used in a list of
two or more items, means that any one of the listed items can be
employed by itself, or any combination of two or more of the listed
items, can be employed. For example, if a composition is described
as containing components A, B, and/or C, the composition can
contain A alone; B alone; C alone; A and B in combination; A and C
in combination; B and C in combination; or A, B, and C in
combination.
[0023] In this document, relational terms, such as first and
second, top and bottom, and the like, are used solely to
distinguish one entity or action from another entity or action,
without necessarily requiring or implying any actual such
relationship or order between such entities or actions. The terms
"comprises," "comprising," or any other variation thereof, are
intended to cover a non-exclusive inclusion, such that a process,
method, article, or apparatus that comprises a list of elements
does not include only those elements but may include other elements
not expressly listed or inherent to such process, method, article,
or apparatus. An element proceeded by "comprises . . . a" does not,
without more constraints, preclude the existence of additional
identical elements in the process, method, article, or apparatus
that comprises the element.
[0024] Aspects of the present disclosure relate to a family of
electrochromic compounds capable of attenuating the transmittance
of at least a portion of the electromagnetic spectrum. The
electrochromic compounds of the present disclosure can be used in
electro-optic elements and electrochromic devices incorporating
such electro-optic elements. The electrochromic compounds of the
present disclosure include a substituted ketal phenazine compound
of Formula (I):
##STR00003##
wherein R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.6, R.sub.7,
R.sub.8, R.sub.9, R.sub.11, and R.sub.12 are individually a
hydrogen, an alkyl, a substituted alkyl, a straight chain alkyl, a
branched alkyl, or a cycloalkyl and R.sub.5 and R.sub.10 are
individually an alkyl, a substituted alkyl, a straight chain alkyl,
a branched alkyl, or a cycloalkyl. In some aspects, one of: (a)
R.sub.5 and R.sub.10, (b) R.sub.11 and R.sub.12, or (c) a
combination of R.sub.5, R.sub.10, R11, and R.sub.12 are
individually an alkyl, a substituted alkyl, a straight chain alkyl,
a branched alkyl, or a cycloalkyl substituted with at least one
polymerizable functional group.
[0025] The substituted ketal phenazine compounds of Formula (I) are
electrochromic and electroactive and thus can be used as an anodic
component in combination with a cathodic component to form
electro-optic elements that can be incorporated into electrochromic
devices. By way of introduction, electrochromic devices generally
include an electrochromic medium that transitions between an
inactivated state in which the electrochromic medium is relatively
transparent to light having a wavelength within a predetermined
wavelength range and an activated state in which the electrochromic
medium has a decreased transmission to light within a predetermined
wavelength range when an electrical potential is applied to the
electrochromic device. The electrochromic medium includes an anodic
component and a cathodic component (also referred to as
electroactive components), at least one of which is also
electrochromic. The electrochromic electroactive component can
provide the electrochromic device with a perceived color when the
electrochromic device is in the activated state and/or as the
device transitions between the inactivated and activated states.
The term "electroactive," as used herein, refers to a material that
can undergo a modification in its oxidation state upon exposure to
a particular electrical potential difference. The term
"electrochromic," as used herein, refers to a material that can
exhibit a change in its extinction coefficient at one or more
wavelengths upon exposure to a particular electrical potential
difference. Electrochromic components, as described herein, include
materials whose color or opacity are affected by an electrical
current, such that when an electrical field is applied to the
material, the color or opacity changes from a first state to a
second state. Thus, an electrochromic device can exhibit a change
in transparency as a result of electrochemical oxidation and
reduction reactions that occur between electroactive components
(i.e., the anodic components and the cathodic components), in which
at least one of the electroactive components is also
electrochromic.
[0026] In some applications, it may be desirable that the
electrochromic device have a perceived neutral or gray color to an
observer in the activated state and/or during the transition
between the activated and inactivated states. For example, with
respect to an electrochromic mirror or window assembly, it may be
desirable that the assembly have a gray color in an activated state
and/or during a transition between activated and inactivated
states. A gray color in the activated state may be perceived by an
observer as interfering less with the images visible in or through
the assembly than other colors. Aspects of the present disclosure
provide an anodic component in the form of the substituted ketal
phenazine compound according to Formula (I) that can be used in
combination with at least one additional anodic component to
provide an electrochromic medium that appears more gray in color
when activated compared to the color exhibited by either of the
anodic components alone.
[0027] Referring to FIGS. 1 and 2A-E, reference numeral 10
generally designates an electrochromic device according to an
aspect of the present disclosure. The electrochromic device 10 can
include a first substrate 70 having a first surface 74 and a second
surface 78, and a first electrically conductive layer 82 disposed
on the second surface 78. A second substrate 86 is provided
opposite the first substrate 70, and includes a third surface 90
and a fourth surface 94. A second electrically conductive layer 98
is disposed on the third surface 90. The first substrate 70 and the
second substrate 86, along with a sealing member 106 define a
chamber 110 for containing an electrochromic medium. The
electrochromic device 10 can also include one or more plugs 130
associated with one or more fill ports. The one or more fill ports
may be disposed within the first substrate 70, the second substrate
86, or the sealing member 106. Upon mounting as a mirror, window,
filter, or other device, the electrochromic device 10 may
optionally include a bezel (not shown) that extends around a
periphery of at least one of the first substrate 70 and/or the
second substrate 86 to conceal and/or protect components of the
electrochromic device 10 and the like, such as a bus connector (if
present), the sealing member 106, one or more plugs 130, and/or the
one or more fill ports.
[0028] In some aspects, the first and second substrates 70, 86 may
be larger than one another or the same in size, but shifted, to
create an offset along at least a portion of the perimeter of the
electrochromic device 10 to allow for easier access to the first
and/or second electrically conductive layers 82, 98. The first
and/or second substrates 70, 86 can be made of glass, plastic, or
other optically transparent or translucent material, non-limiting
examples of which include borosilicate glass, soda lime glass, or
polymeric materials such as natural and synthetic polymeric resins,
plastics, and/or composites including polyesters (e.g. PET),
polyimides (PI), polycarbonates, polysulfones, polyethylene
naphthalate (PEN), ethylene vinyl acetate (EVA), acrylate polymers,
as well as cyclic olefin copolymers (COC) commercially available
from TOPAS.RTM. Advanced Polymers. In some aspects, both the first
and second substrates 70, 86 are made of an optically transparent
or translucent material, while in other aspects, only the first
substrate 70 is made of an optically transparent or translucent
material. The first and second substrates 70, 86 can be made from
the same or different materials and may have the same or different
dimensions. According to some aspects, the second electrically
conductive layer 98 may include a metal reflector or one or more
coatings configured as a partially reflective, partially
transmissive ("transflective") coating. Inclusion of a metal
reflector or a transflective coating may render the electrochromic
device 10 at least partially reflective.
[0029] The first and second electrically conductive layers 82, 98
can include one or more layers of an electrically conductive
material disposed on the first and second substrates 70, 86,
respectively. These layers serve as electrodes (i.e., the cathode
and the anode) for the electrochromic device 10. The electrically
conductive material(s) of the first and/or second electrically
conductive layers 82, 98 may be any suitable material that includes
one or more of the following features: (a) is substantially
transparent to visible and/or IR light; (b) bonds reasonably well
to the first and second substrates 70, 86; (c) maintains the bond
to the first and second substrates 70, 86 when associated with a
sealing member 106; (d) is generally resistant to corrosion from
materials contained within the electrochromic device 10 or the
atmosphere; and/or (e) exhibits minimal diffuse or specular
reflectance as well as sufficient electrical conductance. Depending
on the application, only one of the first and second electrically
conductive layers 82, 98 may be required to be transparent while
the other electrically conductive layer 82, 98 may be opaque. In
some applications, both the first and the second electrically
conductive layers 82, 98 may be transparent. The electrically
conductive material(s) forming the first and second electrically
conductive layers 82, 98 may be the same or different. Non-limiting
examples of electrically conductive material that may be used to
form the first and/or second electrically conductive layers 82, 98
can include fluorine doped tin oxide (FTO), for example TECTM
glass, indium tin oxide (ITO), doped zinc oxide, indium zinc oxide
(IZO), aluminum doped zinc oxide (AZO), and metal oxide/metal/metal
oxide (wherein the metal oxide can be substituted with metal
carbide, metal nitride, metal sulfide, etc . . . ).
[0030] While aspects of the present disclosure are described in the
context of the electrochromic device 10, aspects of the present
disclosure may also be utilized in the context of other
electrochromic devices, non-limiting examples of which include
those disclosed in U.S. Pat. No. 5,818,625, issued Oct. 6, 1998 and
entitled "Electrochromic Rearview Mirror Incorporating a Third
Surface Metal Reflector,"; U.S. Pat. No. 6,597,489, issued Jul. 22,
2003 and entitled "Electrode Design for Electrochromic Devices,";
and U.S. Pat. No. 6,700,692, issued Mar. 2, 2004 and entitled
"Electrochromic Rearview Mirror Assembly Incorporating a
Display/Signal Light," all of which are incorporated herein by
reference in their entirety including all references incorporated
therein.
[0031] Still referring to FIGS. 1 and 2A-E, the electrochromic
device 10 includes an electro-optic element 140 that is at least
partially defined by the first and second substrates 70, 86, the
chamber 110, and the electrochromic medium 124. The electro-optic
element 140 allows the electrochromic device 10 to be operable
between a transparent or clear state, which allows light having a
wavelength within a predetermined wavelength range to pass through,
and a darkened state, in which a portion, or no light having a
wavelength within a predetermined wavelength range, is transmitted
through the electro-optic element 140 (i.e., the electro-optic
element 140 becomes essentially opaque or partially opaque to light
having a wavelength within the predetermined wavelength range). The
electro-optic element 140 may be operable between a substantially
clear state and a substantially dark or darkened state, as well as
intermediate states thereto. The darkened state of the
electro-optic element 140 can be defined relative to the
transmissivity of the substantially clear state. According to an
aspect of the present disclosure, the transmissivity of the
electro-optic element 140 in the substantially transparent or clear
state may be greater than about 25%, greater than about 50%,
greater than about 55%, or greater than about 85%. The percentage
of reflectance, transmittance, and absorbance of the electro-optic
element 140 sum to 100%. In some aspects, the transmissivity of the
electro-optic element 140 in the substantially darkened state may
be less than about 10%, less than about 1%, less than about 0.1%,
less than about 0.01%, or less than about 0.001%.
[0032] The sealing member 106 can traverse an approximate perimeter
of, and is configured to cooperate with, the first and second
substrates 70, 86 to define the chamber 110 as substantially
hermetic. The sealing member 106 may be applied to the first or
second substrates 70, 86 by methods commonly used in the liquid
crystal display (LCD) industry, such as by silk-screening or
dispensing. In one example, the sealing member 106 may incorporate
a first and a second seal as components of the sealing member 106.
In one example, first and second annular bands of highly conductive
material are optionally deposited around the perimeter of the first
and second substrates 70, 86, respectively, and
electrically-conducting structures (e.g., clips or wires) are
secured to the highly conductive material and spatially separated
from one another. The electrically-conducting structures may supply
an electrical voltage to the first and second annular bands of
highly conductive material to create a voltage across the
electro-optic element 140, thereby reversibly driving the
electro-optic element 140 between the substantially dark and
substantially clear states. The first and second annular bands of
highly conductive material may include silver, gold, copper, or
aluminum (such as, for example, in a form of metallic flakes or
particles dispersed in a hosting material).
[0033] Referring to FIGS. 2A-E, the electro-optic element 140
includes an electrochromic medium, at least one cathodic component,
and at least one anodic component. The anodic and cathodic
components may alternatively be referred to as chromophores or
electrochromic molecules. According to some aspects of the present
disclosure, the anodic and/or cathodic components may be a polymer
and/or a monomer. In some aspects, both the cathodic and anodic
components are electroactive and at least the anodic component is
electrochromic.
[0034] According to an aspect of the present disclosure, the anodic
component comprises a substituted ketal phenazine of Formula
(I):
##STR00004##
wherein R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.6, R.sub.7,
R.sub.8, R.sub.9, R.sub.11, and R.sub.12 are individually a
hydrogen, an alkyl, a substituted alkyl, a straight chain alkyl, a
branched alkyl, or a cycloalkyl and R.sub.5 and R.sub.10 are
individually an alkyl, a substituted alkyl, a straight chain alkyl,
a branched alkyl, or a cycloalkyl. In some aspects, both R.sub.5
and R.sub.10, both R.sub.11 and R.sub.12, or a combination of
R.sub.5, R.sub.10, R11, and R.sub.12 are individually an alkyl, a
substituted alkyl, a straight chain alkyl, a branched alkyl, or a
cycloalkyl substituted with at least one polymerizable functional
group. For example, the polymerizable functional group can be a
vinyl group, an acrylate group, a methacrylate group, a vinyl ether
group, a hydroxyl group, an isocyanate group, an oxetane group, an
amine group, and an epoxy group.
[0035] As used herein, "alkyl" groups include straight chain and
branched alkyl groups having from 1 to 20 carbon atoms, from 1 to
12 carbon atoms, from 1 to 8 carbon atoms, from 1 to 6 carbon
atoms, from 6 to 20 carbon atoms, from 6 to 12 carbon atoms, from 8
to 20 carbon atoms, or from 12 to 20 carbon atoms. As employed
herein, "alkyl groups" include cycloalkyl groups as defined below.
Alkyl groups may be substituted or unsubstituted. Examples of
straight chain alkyl groups include methyl, ethyl, n-propyl,
n-butyl, n-pentyl, n-hexyl, n-heptyl, and n-octyl groups. Examples
of branched alkyl groups include isopropyl, sec-butyl, t-butyl,
neopentyl, and isopentyl groups. Representative substituted alkyl
groups may be substituted one or more times with, for example,
amino, thio, hydroxy, cyano, alkoxy, and/or halo groups such as F,
CI, Br, and I groups. As used herein the term haloalkyl is an alkyl
group having one or more halo groups. In some aspects, haloalkyl
refers to a per-haloalkyl group. As used herein, C.sub.m-C.sub.n,
such as C.sub.1-C.sub.12, C.sub.1-C.sub.8, or C.sub.1-C.sub.6, when
used before a group refers to that group containing m to n carbon
atoms.
[0036] As used herein, "substituted" refers to an alkyl group in
which one or more bonds to a hydrogen atom contained therein are
replaced by a bond to non-hydrogen or non-carbon atoms. Substituted
groups also include groups in which one or more bonds to a
carbon(s) or hydrogen(s) atom are replaced by one or more bonds,
including double or triple bonds, to a heteroatom. Thus, a
substituted group will be substituted with one or more
substituents, unless otherwise specified. In some aspects, a
substituted group is substituted with 1, 2, 3, 4, 5, or 6
substituents. Examples of substituent groups include: halogens
(i.e., F, Cl, Br, and I); hydroxyls; alkoxy, alkenoxy, alkynoxy,
aryloxy, aralkyloxy, heterocyclyloxy, and heterocyclylalkoxy
groups; carbonyls (oxo); carboxyls; esters; urethanes; oximes;
hydroxylamines; alkoxyamines; aralkoxya mines; thiols; sulfides;
sulfoxides; sulfones; sulfonyls; sulfonamides; amines; N-oxides;
hydrazines; hydrazides; hydrazones; azides; amides; ureas;
amidines; guanidines; enamines; imides; isocyanates;
isothiocyanates; cyanates; thiocyanates; imines; nitro groups;
nitriles (i.e., CN); and the like. Such substitution includes
solubility enhancing groups as described in U.S. Pat. No.
6,445,486, issued Sep. 3, 2002.
[0037] Cycloalkyl groups are cyclic alkyl groups such as, but not
limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl,
cycloheptyl, and cyclooctyl groups. Cycloalkyl groups may be
substituted or unsubstituted. Cycloalkyl groups further include
polycyclic cycloalkyl groups such as, but not limited to,
norbornyl, adamantyl, bornyl, camphenyl, isocamphenyl, and carenyl
groups, and fused rings, non-limiting examples of which include
decalinyl. Cycloalkyl groups also include rings that are
substituted with straight or branched chain alkyl groups as defined
above. Representative substituted cycloalkyl groups may be
mono-substituted or substituted more than once, non-limiting
examples of which include: 2,2-; 2,3-; 2,4-; 2,5-; or
2,6-disubstituted cyclohexyl groups or mono-, di-, or
tri-substituted norbornyl or cycloheptyl groups, which may be
substituted with, for example, alkyl, alkoxy, amino, thio, hydroxy,
cyano, and/or halo groups.
[0038] In some aspects, the substituted ketal phenazine of the
present disclosure includes at least one substituent including a
polymerizable functional group. Such polymerizable functional
groups allow the substituted ketal phenazine to be covalently
bonded to a polymeric matrix. In one example, one of: (a) a
combination of R.sub.5 and R.sub.10, (b) a combination of R.sub.11
and R.sub.12, or (c) a combination of R.sub.5, R.sub.10, R11, and
R.sub.12 include a polymerizable functional group. Non-limiting
examples of suitable polymerizable functional groups include a
vinyl group, an acrylate group, a methacrylate group, a vinyl ether
group, a hydroxyl group, an isocyanate group, an oxetane group, an
amine group, and an epoxy group. According to one aspect, a
combination of both R.sub.5 and R.sub.10, a combination of both
R.sub.11 and R.sub.12, or a combination of R.sub.5, R.sub.10,
R.sub.11, and R.sub.12can individually be a C.sub.1-C.sub.20 alkyl
group including at least one substituted polymerizable functional
group. For example, the alkyl group can include from 1 to 20 carbon
atoms, from 1 to 12 carbon atoms, from 1 to 8 carbon atoms, from 1
to 6 carbon atoms, from 6 to 20 carbon atoms, from 6 to 12 carbon
atoms, from 8 to 20 carbon atoms, or from 12 to 20 carbon atoms
linking the polymerizable functional group with the substituted
ketal phenazine. The alkyl group can be a straight chain alkyl, a
branched alkyl, a cycloalkyl, or a substituted alkyl.
[0039] In some aspects of the present disclosure, at least one of
the groups R.sub.2, R.sub.5, R.sub.7, and R.sub.10 is free of beta
hydrogens. In one example, all of the groups R.sub.2, R.sub.5,
R.sub.7, and R.sub.10 are free of beta hydrogens such that the
substituted ketal phenazine according to Formula (I) is free of
beta hydrogens. In one aspect, R.sub.5 and R.sub.10 are free of
beta hydrogens, R.sub.2 and R.sub.7 are free of beta hydrogens, or
R.sub.2, R.sub.5, R.sub.7, and R.sub.10 are all free of beta
hydrogens. Neopentyl and 1-adamantane methyl are examples of
substituent groups that are free of beta hydrogens. FIGS. 3A and 3B
illustrate exemplary substituted ketal phenazine compounds,
4-(2-tert-butyl-2-{7-[2-tert-butyl-4-(4-hydroxylbutyl)-1,3-dioxolan-2-yl}-
-5,10-bis(2,2-dimethylpropyl)
phenazine-2-yl)-1,3-dioxolan-4-yl}butane-1-ol ("Compound (I)") and
4-(2-tert-butyl-2-{7-[2-tert-butyl-4-(4-hydroxymethyl)-1,3-dioxolan-2-yl]-
-5,10-bis(2,2-dimethylpropyl) phenazine-2-yl}-1,3-dioxolan-4-yl)
methanol ("Compound (II)"), according to Formula (I), in which the
groups R.sub.5, and R.sub.10 are neopentyl groups and the groups
R.sub.2 and R.sub.7 are tertiary alkyl groups, and thus Compounds I
and II are both free of beta hydrogens. Compound (II) is similar to
Compound (I) except that the alkyl chain coupling the hydroxyl
functional group to the ketal includes fewer carbons. Without being
limited by any theory, it is believed that the absence of beta
hydrogens can increase a stability of the substituted ketal
phenazine according to Formula (I), especially in applications in
which the substituted ketal phenazine is exposed to ultraviolet
(UV) light, such as in electrochromic windows and sunroofs, for
example.
[0040] In some aspects of the present disclosure, the substituted
ketal phenazines according to Formula (I) can be characterized by a
maximum absorbance at about 400 nm to about 550 nm, when oxidized
(i.e., when in the activated state). For example, the substituted
ketal phenazines according to Formula (I) can be characterized by a
maximum absorbance of about 410 nm to about 550 nm, about 420 nm to
about 550 nm, about 430 nm to about 550 nm, about 440 nm to about
550 nm, about 450 nm to about 550 nm, about 460 nm to about 550 nm,
about 470 nm to about 550 nm, about 480 nm to about 550 nm, about
490 nm to about 550 nm, 410 nm to about 500 nm, about 420 nm to
about 500 nm, about 430 nm to about 500 nm, about 440 nm to about
500 nm, about 450 nm to about 500 nm, about 460 nm to about 500 nm,
about 470 nm to about 500 nm, about 480 nm to about 500 nm, about
490 nm to about 500 nm, when oxidized. In one example, the
substituted ketal phenazines according to Formula (I) can be
characterized by a maximum absorbance of about 450 nm, about 455
nm, about 460 nm, about 465 nm, about 470 nm, about 475 nm, about
480 nm, about 485 nm, about 490 nm, about 500 nm, or any value
between these values, when oxidized.
[0041] In some aspects of the present disclosure, the substituted
ketal phenazines according to
[0042] Formula (I) can be characterized by an oxidation potential
of about 300 mV. For example, the substituted ketal phenazines
according to Formula (I) can be characterized by an oxidation
potential of about 270 mV to about 325 mV, about 275 mV to about
325 mV, about 280 mV to about 325 mV, about 285 mV to about 325 mV,
about 290 mV to about 325 mV, about 295 mV to about 325 mV, about
300 mV to about 325 mV, about 305 mV to about 325 mV, about 310 mV
to about 325 mV, about 270 mV to about 315 mV, about 275 mV to
about 315 mV, about 280 mV to about 315 mV, about 285 mV to about
315 mV, about 290 mV to about 315 mV, about 295 mV to about 315 mV,
about 300 mV to about 315 mV, about 305 mV to about 315 mV, 270 mV
to about 300 mV, about 275 mV to about 300 mV, about 280 mV to
about 300 mV, about 285 mV to about 300 mV, or about 290 mV to
about 300 mV. In some examples, the substituted ketal phenazines
according to Formula (I) can be characterized by an oxidation
potential of about 270 mV, about 275 mV, about 280 mV, about 285
mV, about 290 mV, about 295 mV, about 300 mV, about 305 mV, about
310 mV, about 315 mV, about 320 mV, about 325 mV, or any value
between these values.
[0043] In some aspects, an electrochromic medium according to an
aspect of the present disclosure includes a substituted ketal
phenazine according to Formula (I) in combination with at least one
additional anodic component(s) such that when oxidized, the
combination of anodic components exhibit a neutral gray color to an
observer. For example, a substituted ketal phenazine according to
Formula (I) can be combined with one or more additional anodic
phenazine compounds such that when oxidized, the combination of
anodic components exhibit a neutral gray color. The color of the
electrochromic medium can be characterized using CIE LAB color
coordinates. The CIE LAB color space defines the color of a
material using the lightness value L* and color coordinates a* and
b*. An L* value of 0 in CIELAB color space represents the darkest
black and an L* value of 100 is indicative of the brightest white.
The a* axis in color space is representative of the green-red color
component, with negative a* values corresponding to green and
positive a* values corresponding to red. The b* axis in color space
is representative of the blue-yellow component, with negative b*
values corresponding to blue and positive b* values corresponding
to yellow. The closer the a* and b* values are to the origin, the
more gray (i.e., neutral) in color the aperture structure will
appear to an observer.
[0044] For example, an electrochromic medium according to an aspect
of the present disclosure can include a substituted ketal phenazine
according to Formula (I) in combination with at least one
additional anodic component(s) such that when oxidized, the
electrochromic medium is characterized by an a* value of about 0 to
about .+-.25, about 0 to about .+-.20, about 0 to about .+-.15,
about 0 to about .+-.10, or about 0 to about .+-.5 and a b* value
of about 0 to about .+-.25, about 0 to about .+-.20, about 0 to
about .+-.15, about 0 to about .+-.10, or about 0 to about .+-.5,
when illuminated with a D65 series illuminant (representing natural
daylight) at an angle of incidence (A01) of 2 degrees. In one
example, the electrochromic medium is characterized by an a* and a
b* value that are individually, about 0, about .+-.5, about .+-.10,
about .+-.15, about .+-.20, about .+-.25, or any value between
these values when illuminated with a D65 series illuminant and an
AOI of 2 degrees.
[0045] In one aspect, an electrochromic medium according to an
aspect of the present disclosure can include a substituted ketal
phenazine according to Formula (I) in combination with at least one
additional anodic component(s) and at least one electrochromic
cathodic component such that when the electrochromic components are
activated (i.e., the anodic components are oxidized and the
cathodic components are reduced), the electrochromic medium is
characterized by an a* value of about 0 to about .+-.25, about 0 to
about .+-.20, about 0 to about .+-.15, about 0 to about .+-.10, or
about 0 to about .+-.5 and a b* value of about 0 to about .+-.25,
about 0 to about .+-.20, about 0 to about .+-.15, about 0 to about
.+-.10, or about 0 to about .+-.5, when illuminated with a D65
series illuminant and an AOI of 2 degrees. In one example, the
electrochromic medium is characterized by an a* and a b* value that
are individually, about 0, about .+-.5, about .+-.10, about .+-.15,
about .+-.20, about .+-.25, or any value between these values when
illuminated with a D65 series illuminant and an AOI of 2 degrees.
For example, a substituted ketal phenazine according to Formula (I)
can be combined with at least one additional anodic phenazine and a
cathodic viologen.
[0046] According to one aspect, an oxidation potential of the
substituted ketal phenazine according to Formula (I) and the
oxidation potential of each of the additional anodic component(s)
are within .+-.60 mV. Selecting anodic components such that the
oxidation potentials are near one another may facilitate achieving
a consistent observable color appearance during darkening and
clearing of the electrochromic device during operation. In some
examples, an oxidation potential of the substituted ketal phenazine
according to Formula (I) and an oxidation potential of each of the
additional anodic component(s) can be selected to be within .+-.60
mV, within .+-.55 mV, within .+-.50 mV, within .+-.45 mV, or within
.+-.40 mV.
[0047] The present substituted ketal phenazine compounds of Formula
(I) can be utilized in solution form, gel form, or film form as the
anodic component in an electrochromic medium of an electro-optic
element. The electrochromic medium may include layers of materials
attached directly to an electrically conductive layer or confined
in close proximity to an electrically conductive layer which
remains attached or confined when components thereof are oxidized
and/or reduced.
[0048] In one aspect, the substituted ketal phenazine compounds of
Formula (I) may be incorporated into a polymeric film to form an
anodic film. The present substituted ketal phenazine compounds can
be incorporated into the backbone of the polymeric chains forming
the polymeric film and/or covalently bonded to the polymeric chains
as pendant groups. For example, the anodic film may be a polymeric
film including a plurality of polymeric chains composed of a number
of repeating monomer units forming a backbone of the polymer
chains. The cathodic film may include a binder polymer (e.g.,
polymethylmethacrylate, PMMA, polyvinyl formal, or polyethylene
glycol), a plasticizer that will help facilitate ion conductivity
(e.g., propylene carbonate or gamma-butyrolactone) and a supporting
electrolyte (e.g., tetraethylammonium tetrafluoroborate or lithium
hexafluorophosphate). The substituted ketal phenazine compounds of
Formula (I) may form pendant groups attached to the polymer
backbone or be disposed between the monomer units of the
backbone.
[0049] According to one aspect, the substituted ketal phenazine
compounds of Formula (I) can include a hydroxyl group, such that
the compound may be bound into a polymer matrix via a condensation
reaction or react with an isocyanate functionality to form a
polyurethane-based polymer matrix. Amines may also react with
isocyanate functionalities to form urea and biuret linkages. It is
also within the scope of the present disclosure to utilize other
polymeric matrix systems that contain compounds of Formula (I) that
can be formed using a multi-functional epoxy in combination with a
curing agent like an amine, alcohol, or anhydride or through base
or acid catalyzed homo-polymerization. Non-limiting examples of
materials that may be used as a polymeric matrix for covalently
bonding with the substituted ketal phenazine compounds of Formula
(I) include: polymethylmethacrylate, polypropylene methacrylate,
polystyrene, polyurethanes, polyethers, polyesters, polycarbonates,
polysiloxanes, polysilanes, polyacrylonitriles,
polymethacrylonitriles, polyamides, polyimides, polyvinylidene
halides, and co-polymer and combinations of thereof. Further
examples of polymer matrix materials can be found in U.S. Pat. Nos.
6,635,194; 5,940,201; 5,928,572; and 9,964,828, which are herein
incorporated by reference in their entirety.
[0050] In another aspect, the anodic film may be a solid polymer or
a gel polymer. For example, the polymer may be an acrylate-based
polymer that is dissolved in a solvent which incorporates the
substituted ketal phenazine compounds of Formula (I). This solution
is then coated on the conductive surface of a substrate, followed
by removal of the solvent. The resultant film is an acrylate film
that may be hard or tacky to the touch. In another example, the
polymer film may be a gel that contains solvent as well as the
substituted ketal phenazine compounds of Formula (I). Optionally,
the polymer film maybe subsequently cross-linked for increased
mechanical stability. Other non-limiting examples of polymer matrix
systems that could be used with the substituted ketal phenazine
compounds of Formula (I) include: polyacrylate, polymethacrylates,
polyethers, polyesters, polycarbonates, polyurethanes,
polysiloxanes, polysilanes, polyacrylonitriles, polystyrenes,
polymethacrylonitriles, polyamides, polyimides, polyvinylidene
halides, and co-polymers, or combinations of any two or more
thereof. Further examples of polymer matrix materials used in
electrochromic devices can be found in U.S. Pat. Nos. 6,635,194;
5,940,201; 5,928,572; and 9,964,828, which are herein incorporated
by reference in their entirety.
[0051] The electrochromic medium can include one or more anodic
components in addition to the substituted ketal phenazines of the
present disclosure, examples of which include: metallocenes,
5,10-dihydrophenazines, phenothiazines, phenoxazines, carbazoles,
triphenodithiazines, triphendioxazines, ferrocene, substituted
ferrocenes, substituted ferrocenyl salts, phenazine, substituted
phenazines, phenothiazine, substituted phenothiazines, including
substituted dithiazines, thianthrene and substituted thianthrenes,
di-tert-butyl-diethylferrocene, 5,10-dimethyl-5,10-dihydrophenazine
(DMP), 3,7,10-trimethylphenothiazine,
2,3,7,8-tetramethoxy-thianthrene, 10-methylphenothiazine,
tetramethylphenazine (TMP),
bis(butyltriethylammonium)-para-methoxytriphenodithiazine (TPDT),
3,10-dimethoxy-7,14-(triethylammoniumbutyl)-triphenodithazinebis(tetraflu-
oroborate), and combinations thereof. Additional examples of anodic
components that can be used in combination with the substituted
ketal phenazines of the present disclosure include a substituted or
unsubstituted 2,7-dialkyl-5,10-dialkyl-5,10-dihydrophenazine
compound. In another example, at least one alkyl group of the
5,10-dialkyl groups attached to the phenazine compound includes at
least 4 carbon atoms and is void of any .beta. hydrogen atoms, and
at least one alkyl group of the 2,7-dialkyl groups attached to the
phenazine compound includes at least 4 carbons. In another example,
at least one alkyl group of the 5,10-dialkyl groups attached to the
phenazine compound includes a substituted or unsubstituted
neopentyl group, and at least one alkyl group of the 2,7-dialkyl
groups attached to the phenazine compound includes a substituted or
unsubstituted isopropyl, isobutyl, (2-ethylbutyl), or
(2-propylpentyl) group. In another example, at least one alkyl
group of the 5,10-dialkyl groups attached to the phenazine compound
includes a neopentyl group, and at least one alkyl group of the
2,7-dialkyl groups attached to the phenazine compound includes a
2-ethyl-1-butanol group. In yet another example, at least one alkyl
group of the 5,10-dialkyl groups attached to the phenazine compound
includes a neopentyl group, and at least one alkyl group of the
2,7-dialkyl groups attached to the phenazine compound includes an
isobutyl group. The one or more additional anodic components may be
incorporated into a polymeric film to form an anodic film in a
manner similar to that described above with respect to the
substituted ketal phenazines of the present disclosure. The one or
more additional anodic components can be incorporated into the
backbone of the polymeric chains forming the polymeric film and/or
covalently bonded to the polymeric chains as pendant groups. The
substituted ketal phenazines of the present disclosure and the one
or more additional anodic components can be incorporated into the
same polymeric film or separate polymeric films.
[0052] The cathodic component of the electrochromic medium can be
any suitable solvent, film, or gel-based material having a cathodic
component incorporated therein capable of cooperating with the
substituted ketal phenazine compounds of Formula (I) to form an
electro-optic element. The cathodic component can include a
reducible compound, non-limiting examples of which include a
viologen, a low-dimerizing viologen, or a non-dimerizing viologen.
Illustrative viologens include, but are not limited to, methyl
viologen, octyl viologen, benzyl viologen, polymeric viologens, and
the viologens described in U.S. Pat. Nos. 4,902,108; 6,188,505;
5,998,617; 9,964,828; and 6,710,906, which are herein incorporated
by reference in their entirety. In one aspect, the cathodic
component is selected from a viologen, a low-dimerizing viologen, a
non-dimerizing viologen, a substituted viologen, a di-acrylate
viologen, a cathodic di-vinyl viologen, a cathodic di-vinyl ether
viologen, a cathodic di-epoxy viologen, a cathodic di-oxetane
viologen, a cathodic di-hydroxy viologen, or a combination thereof.
The cathodic component may be incorporated into a polymeric film to
form a cathodic film. The cathodic component can be incorporated
into the backbone of the polymeric chains forming the polymeric
film and/or covalently bonded to the polymeric chains as pendant
groups in a manner similar to that described above with respect to
the anodic film. In some examples, the electrochromic medium may
include a combination of two or more cathodic components to provide
the electrochromic medium with the desired color when activated.
Examples of suitable combinations of anodic and cathodic components
can be found in U.S. Patent No. 6,020,987, entitled "Electrochromic
Medium Capable of Producing a Pre-Selected Color," issued Feb. 1,
2000, the contents of which are incorporated herein by reference in
their entirety.
[0053] Without being limited by any theory, it is believed that
immobilizing the anodic components and the cathodic components,
such as by incorporating the anodic components and cathodic
components into a polymeric matrix, inhibits the activated anodic
and activated cathodic components from undergoing charge transfer
processes that may lead to clearing of the electrochromic device.
Typically, upon charging of a traditional solution-phase
electrochromic device, internal diffusion processes may result in
charge transfer reactions that result in clearing of the device
upon removal of the electric potential. Immobilizing the anodic
components and the cathodic components can result in the
electrochromic device maintaining its darkened (colored) state for
longer periods of time upon removal of the electric potential
compared to a solution phase device incorporating the same anodic
and cathodic components.
[0054] According to some aspects, a concentration of the substitute
ketal phenazine compounds of Formula (I), the one or more
additional anodic components, and/or the cathodic component in the
electrochromic medium can be from about 1 millimolar (mM) to about
500 mM, from about 2 mM to about 100 mM, about 5 mM to about 50 mM,
about 40 mM to about 50 mM, about 60 mM to about 90 mM, or about 70
mM to about 80 mM. In one aspect, a concentration of the cathodic
component is about 50 mM, about 50 mM to about 100 mM, about 60 to
about 90 mM, or about 70 mM to about 80 mM. In one aspect, a
concentration of any of the anodic components present in the
electrochromic medium is at least 5 mM or about 2 mM to about 100
mM, about 5 mM to about 50 mM, or about 7 mM to about 50 mM. When
more than one anodic component is present, a concentration of each
of the anodic components may be determined individually.
[0055] The electrochromic medium may also include an electrolyte,
which may be in the form of a solvent and a salt. The salt may be a
metal salt or an ammonium salt. Non-limiting examples of suitable
solvents for use in the electrolyte include: 3-methylsulfolane,
dimethyl sulfoxide, dimethyl formamide, tetraglyme, and other
polyethers; alcohols such as ethoxyethanol; nitriles, such as
acetonitrile, glutaronitrile, 3-hydroxypropionitrile, and
2-methylglutaronitrile; ketones including 2-acetylbutyrolactone,
and cyclopentanone; cyclic esters including beta-propiolactone,
gamma-butyrolactone, and gamma-valerolactone; propylene carbonate
(PC), ethylene carbonate; and homogenous mixtures thereof.
Non-limiting examples of suitable salts include: metal or ammonium
salts, such as Li.sup.+, Na.sup.+, K.sup.+, NR'.sub.4.sup.+ (where
each R' is individually H, alkyl, or cycloalkyl), of the following
anions F.sup.-, Cl.sup.-, Br.sup.-, I.sup.-, BF.sub.4.sup.-,
PF.sub.6.sup.-, SbF.sub.6.sup.-, AsF.sub.6.sup.-, ClO.sub.4.sup.-,
SO.sub.3CF.sub.3.sup.-, N(CF.sub.3SO.sub.2).sub.2 ,
C(CF.sub.3SO.sub.2).sub.3.sup.-, N(SO.sub.2C.sub.2F.sub.5).sup.-,
Al(OC(CF.sub.3).sub.3).sub.4.sup.-, or BAr.sub.4.sup.-, wherein Ar
is an aryl or fluorinated aryl group such as, but not limited to,
C.sub.6H.sub.5, 3,5-(CF.sub.3).sub.2C.sub.6H.sub.3, or
C.sub.6F.sub.5.
[0056] The electrochromic medium may optionally include additional
materials, such as light absorbers, light stabilizers, thermal
stabilizers, antioxidants, oxygen scavengers, thickeners, viscosity
modifiers, tint providing agents, redox buffers, and mixtures of
any two or more such materials. Non-limiting examples of
UV-stabilizers may include ethyl-2-cyano-3,3-diphenyl acrylate;
(2-ethylhexyl)-2-cyano-3,3-diphenyl acrylate;
2-(2'-hydroxy-4'-methylphenyl)benzotriazole, sold by Ciba-Geigy
Corp. under the trademark Tinuvin.RTM. P;
3-[3-(2H-benzotriazole-2-yl)-5-(1,1-dimethylethyl)-4-hydroxyphenyl]propio-
nic acid pentyl ester prepared from Tinuvin.RTM. 213, sold by
Ciba-Geigy Corp., via conventional hydrolysis followed by
conventional esterification (hereinafter "Tinuvin.RTM. PE");
2,4-dihydroxybenzophenone; 2-hydroxy-4-methoxybenzophenone; and
2-ethyl-2'-ethoxyalanilide.
[0057] FIGS. 2A, 2C, and 2D illustrate exemplary configurations of
the electro-optic element 140 including a cathodic film 122 wherein
the cathodic component is covalently bound into the film. As
illustrated in FIG. 2A, the cathodic film 122 can be utilized in an
electro-optic element 140 in combination with an anodic solution or
gel 126 including the substituted ketal phenazine anodic component
according to Formula (I) and optionally at least one additional
anodic component. The cathodic film 122 can be disposed on the
first electrically conductive layer 82 while the anodic solution or
gel 126 can be disposed on the second electrically conductive layer
98. Optionally, the relative locations of the cathodic film 122 and
the anodic solution or gel 126 can be reversed.
[0058] Additionally, the anodic solution or gel 126 may contain one
or more electrolytes configured to facilitate electrical
communication of the first and second electrically conductive
layers 82, 98 across the anodic solution or gel 126 and cathodic
film 122. The anodic solution or gel 126 may be in a semi-liquid
state capable of ionically transporting the anodic component to the
cathodic component within the cathodic film 122. For example, the
anodic solution or gel 126 may permeate the cathodic film 122 with
the one or more electrolytes and/or anodic components.
[0059] FIG. 2B illustrates an exemplary configuration of the
electro-optic element 140 including a cathodic solution or gel 138.
As illustrated in FIG. 2B, the cathodic solution or gel 138 can be
utilized in the electro-optic element 140 with an anodic film 134,
as illustrated in FIGS. 2B-D. The cathodic solution or gel 138 can
be disposed on the first electrically conductive layer 82, while
the anodic film 134 can be disposed on the second electrically
conductive layer 98, or vice versa. The cathodic solution or gel
138 can be an electrochromic gel that may contain one or more
electrolytes configured to facilitate electrical communication of
the first and second electrically conductive layers 82, 98 across
the cathodic solution or gel 138 and anodic film 134. According to
one aspect, the cathodic solution or gel 138 may be in a
semi-liquid state capable of ionically transporting the cathodic
component to the anodic component within the anodic film 134. For
example, the cathodic solution or gel 138 may permeate the anodic
film 134 with the one or more electrolytes and/or cathodic
components. In the depicted example, either or both of the anodic
and cathodic components of the anodic film 134 and cathodic
solution or gel 138, respectively, may be electrochromic.
[0060] The anodic film 134 can be any suitable film incorporating
the substituted ketal phenazine anodic component according to
Formula (I) and optionally at least one additional anodic
component. In examples of the of the electro-optic element 140
including the anodic film 134, the substituted ketal phenazine
anodic component according to Formula (I) and the optional at least
one additional anodic component may be disposed between the monomer
units of the backbone and/or present as pendant groups on the
polymer chain.
[0061] Referring now to the example depicted in FIG. 2C, the
electro-optic element 140 includes both the cathodic film 122 and
the anodic film 134. The cathodic film 122 and the anodic film 134
may be in direct contact with one another, or may be separated
(e.g., by a film which is configured to promote electrical
isolation or ion exchange). As explained above, the cathodic and
anodic films 122, 134 may be polymeric films including the cathodic
component and anodic component disposed along the backbone, or as
pendant groups, of the polymeric chains of the cathodic and anodic
films 122, 134, respectively.
[0062] Referring now to the example depicted in FIG. 2D, the
electro-optic element 140 includes both the cathodic film 122 and
the anodic film 134 in addition to an electrolyte layer 146
separating the films 122, 134. The electrolyte layer 146 may be a
gel (e.g., a semi-liquid configured to permeate the cathodic and
anodic films 122, 134) or polymeric electrolyte. In examples
utilizing a polymeric electrolyte as the electrolyte layer 146, the
polymeric electrolyte may include poly(styrene-ran-ethylene),
polystyrene-block-poly(ethylene-ran-butylene),
poly(styrene-ran-ethylene),
polystyrene-block-poly(ethylene/butylene)-block-polystyrene,
poly(ethylene glycol), poly(methyl methacrylate), other polymer
electrolytes and/or combinations thereof. The electrolyte layer 146
may partially permeate the cathodic and anodic films 122, 134.
[0063] Referring now to the example depicted in FIG. 2E, the
electro-optic element 140 may include an electro-optic film 154.
The electro-optic film 154 may be a polymeric material composed of
a plurality of polymeric chains, similar to the cathodic and anodic
films 122, 134 (FIGS. 2C and 2D). In such an example, the
electro-optic film 154 may contain both the anodic component and
the cathodic component on the backbones of the polymeric chains,
and/or as pendant groups. In some examples, the anodic component
and cathodic component may both be positioned on the same polymer
chains, while in other examples, the anodic component and cathodic
component may be positioned on separate polymeric chains.
Alternatively, the electro-optic film 154 may be a solution or a
gel that contains both anodic and cathodic materials not bound to a
polymer, but free to diffuse through the electro-optic film
154.
[0064] The substituted ketal phenazines of the present disclosure
may be utilized in electrochromic mediums for electro-optic
elements that may be utilized in a variety of different
electrochromic devices, non-limiting examples of which include
interior and exterior mirror assemblies, interior and exterior
windows, display screens, heads-up displays, vehicle window
assemblies, architectural window assemblies, filter assemblies, eye
wear, cameras, and display boards.
[0065] The following examples describe various features and
advantages provided by the disclosure, and are in no way intended
to limit the invention and appended claims.
EXAMPLES
Example 1
[0066] FIG. 4 illustrates an exemplary synthetic scheme 200 for
synthesizing the substituted ketal phenazine Compound (I) of FIG.
3A. While the synthesis is discussed in the context of Compound
(I), it is understood that the synthesis process is applicable to
other substituted ketal phenazines of Formula (I). It is also
understood that Compound (I) may synthesized according to other
processes. It is also understood that the synthetic scheme 200 may
include additional or alternative steps without deviating from the
scope of the present disclosure.
[0067] Still referring to FIG. 4, step 202 is a Friedel-Crafts
diacylation of 5,10-dineopentyl-5,10-dihydrophenazine (A) to
produce 2,7-trimethyl acetyl-5,10-dineopentyl-5,10-dihydrophenazine
(B). It is possible to form a mixture of isomers at this step, for
example diacylation at the 2,6 positions, the 2,8 positions, and
the 2,9 positions. At step 202, 25 grams of
5,10-dineopentyl-5,10-dihydrophenazine, 4.36 grams of zinc
chloride, 43.3 grams of pivalic anhydride, and 300 milliliters (ml)
dichloroethane were charged in a 1 liter reaction flask and heated
to reflux for 15 hours. The reaction mixture was then cooled to
room temperature. 200 ml of a 1 Normal dilute hydrochloric acid
solution was slowly added to the reaction mixture. The reaction
mixture was then heated to 70.degree. C. for four hours and then
cooled to room temperature. The reaction mixture was transferred to
separatory funnel, the aqueous layer was removed, and the organic
layer was transferred to a reaction flask. To this reaction flask,
150 ml of water and 10 ml of 50% sodium hydroxide solution was
added and the mixture was stirred for 4 hours. The reaction mixture
was transferred to a separatory funnel and the organic layer was
separated. Solvent was distilled off to give a solid which was
recrystallized from 100 ml hexane to give 25.8 g of 2,7-trimethyl
acetyl-5,10-dineopentyl-5,10-dihydrophenazine (B).
[0068] 5,10-dineopentyl-5,10-dihydrophenazine can be synthesized as
described in Examples 2 and 3 of U.S. Pat. No. 7,428,091, issued
Sep. 23, 2008 and entitled "Electrochromic Compounds and Associated
Media and Devices", the contents of which are incorporated herein
by reference in their entirety.
[0069] At step 204, 2,7-trimethyl
acetyl-5,10-dineopentyl-5,10-dihydrophenazine (B) is reacted with
1,2,6-hexanetriol in an acid catalyzed ketalization process to form
4-(2-tert-butyl-2-1-{7-[2-tert-butyl-4-(4-hydroxylbutyl)-1,3-dioxolan-2-y-
l1-5,10-bis(2,2-dimethylpropyl)
phenazine-2-yl)-1,3-dioxolan-4-yl}butane-1-ol (Compound (I)). Step
204 involves charging 10 grams of 2,7-trimethyl
acetyl-5,10-dineopentyl-5,10-dihydrophenazine, 10 grams of
1,2,6-hexane triol, 0.3 grams of p-toluene sulfonic acid, and 300
ml toluene to a 500 ml 3-neck round bottom flask equipped with a
Dean-Stark condenser. The reaction mixture was refluxed for 48
hours and then cooled to room temperature. To this reaction
mixture, 100 ml of dilute sodium dithionite solution was added and
the mixture was transferred to a separatory funnel. The organic
layer was separated and solvent was removed to give an oil. To this
oil 200 ml hexane was added and the mixture was cooled to 5.degree.
C. over night. The solid was filtered to yield about 8.9 gram of
Compound (I).
[0070] Compound (II) of FIG. 3B can be synthesized using step 202
to generate trimethyl acetyl-5,10-dineopentyl-5,10-dihydrophenazine
(B). Compound (II) can be produced from structure (B) by charging 3
grams of 2,7-trimethyl
acetyl-5,10-dineopentyl-5,10-dihydrophenazine (B), 8.3 grams of
anhydrous glycerol, 0.2 grams of p-toluene sulfonic acid, and 150
ml toluene to a 250 ml 3-neck round bottom flask equipped with a
Dean-Stark condenser. The reaction mixture was refluxed for 72
hours and then cooled to room temperature. To this mixture, 100 ml
of dilute sodium dithionite solution was added and the mixture was
transferred to a reparatory funnel. The solvent was removed to
yield about 3.5 gram of
4-(2-tert-butyl-2-1-{7-[2-tert-butyl-4-(4-hydroxymethyl)-1,3-dioxolan-2-y-
l]-5,10-bis(2,2-dimethylpropyl) phenazine-2-yl}-1,3-dioxolan-4-yl)
methanol (Compound (II)).
Example 2
[0071] FIG. 5 is a plot comparing the absorbance of a radical
cation of the exemplary substituted ketal phenazine Compound (I) of
FIG. 3A and a radical cation of a comparative phenazine compound
(Comparative Compound (I)) shown below:
##STR00005##
[0072] where PF.sub.6.sup.- is a hexafluorophosphate
counterion.
[0073] The experimental set-up for the sample electrochemical cell
used to generate the data shown in FIGS. 6-7 is as follows:
[0074] A sample of Comparative Compound (I) ("Comparative Example
1A") was prepared by coating an indium tin oxide (ITO) coated piece
of four 3''.times.3'' glass sections (2.2 mm thickness) with a
mixture made by dissolving 0.16 grams of bis (11-hydroxyundecyl)
viologen bis[hexafluorophosphate] (PF.sub.6), 0.186 grams of bis
(6-hydroxyhexyl) viologen bis[bis trifluoromethanesulfonyl imide]
(NTF), 0.0006 grams of surfactant (TEGO Glide 410), and 0.134 grams
of HDT in a 3 gram solution in propylene carbonate (PC) and
3-methoxypropionitrile (MPN) (35% wt PC, 65% wt MPN), plus 20
microliters of a 0.6 percent by weight (% wt) solution of
dibutyltin diacetate (DBTDA) catalyst in PC thereby forming a first
film. This coating was made using a #16 Mayer rod to control
thickness. A second piece of four 3''.times.3'' glass sections (2.2
mm thickness) was coated with a solution made by dissolving 0.317
grams of phenazine, 0.001 grams of surfactant (TEGO Glide 450), and
0.133 grams of HDT in a 2 gram solution in propylene carbonate (PC)
and 3-methoxypropionitrile (MPN) (35% wt PC, 65% wt MPN), plus 14
microliters of a 0.6% wt solution of DBTDA catalyst in PC, thereby
forming a second film. This second film was made using a #8 Mayer
rod to control thickness.
[0075] A sample of Compound (I) ("Example 1A") was prepared by
coating an indium tin oxide (ITO) coated piece of four
3''.times.3'' glass sections (2.2 mm thickness) with a mixture made
by dissolving 0.16 grams of bis(11-hydroxy undecyl) viologen
bis[hexafluorophosphate] (PF.sub.6), 0.186 grams of bis
(6-hydroxyhexyl)viologen bis[bistrifluoromethane sulfonyl imide]
(NTF), 0.0006 grams of surfactant (TEGO Glide 410), and 0.134 grams
of HDT in a 3 gram solution in propylene carbonate (PC) and
3-methoxypropionitrile (MPN) (35%PC, 65% MPN) plus 20 microliters
of a 0.6% wt solution of dibutyl tin diacetate (DBTA) catalyst in
PC, thereby forming the first film. This coating was made using #16
Mayer rod to control the thickness. A second piece of 3''.times.3''
glass sections (2.2 mm thickness) was coated with a mixture made
with a solution made by dissolving 0.209 grams of ketal phenazine
Compound (I), 0.105 grams of
N,N'-bis[dimethyl(2-propanol)]-1,6-hexyl ammonium di[bis
(trifluoromethane sulfonamide)], 0.001 grams of surfactant (TEGO
Glide 450), and 0.136 grams of HDT in 2 gram solution in 40% wt
cyclohexanone, 30% wt diacetone alcohol, 20% wt ethylene glycol
diacetate, and 10% wt butyl carbitol acetate, plus 34 microliters
of DBTA in PC, thereby forming a second film. This second film was
made with a #8 Mayer rod.
[0076] The films were allowed to cure under a nitrogen atmosphere
overnight in an oven at 60.degree. C. The first and second films on
their respective glass substrates were positioned in a space-apart
relationship facing each other and an epoxy seal was placed around
the perimeter and cured to form a cell leaving offsets for
attachment of electrical contacts. The distance between the two
substrates was about 135 micrometers. The resulting cell was filled
with a solution of 0.1 molar tetraethyl ammonium tetrafluoroborate
(TEABF.sub.4) and a cross-linkable polymer matrix precursor in PC
to form a polymeric electrolyte.
[0077] The absorbance of a radical cation of Compound (I) (Example
1A) and a radical cation of Comparative Compound (I) (Comparative
Example 1A) was measured over a working optical range of about 385
nm to about 785 nm. The radical cation of Compound (I) and
Comparative Compound (I) represent the oxidized species that would
be present in an electrochromic device utilizing these compounds as
the anodic component. The radical cation for Example 1A and
Comparative Example 1A was oxidized by applying a potential to the
sample electrochemical cell formed as described above. The working
electrode was a piece of glass with half-wave ITO coating, the
reference electrode was a silver wire pseudo reference electrode,
and the counter electrode was a platinum mesh. A Gamry interface
1010E potentiostat was used to apply a potential of +305 mV versus
the silver wire pseudo reference electrode. A USB4000 spectrometer
was used to collect the spectra.
[0078] Compound (I) exhibits a red shift in its maximum absorbance
(X.sub.max) compared to a maximum absorbance of Comparative
Compound (I) of about 22 nm. The overlap in maximum absorbance
exhibited by Compound (I) and Comparative Compound (I) indicates
that these compounds could be used in combination as the anodic
component in an electrochromic device to produce a color that is
more gray (i.e., more neutral in appearance) than Comparative
Compound (I) alone.
Example 3
[0079] FIG. 6 is a plot comparing the absorbance of an exemplary
electrochromic device (Example 2A) and a comparative electrochromic
device (Comparative Example 2A). Both devices include a similar
structure and components, except that Example 2A includes the
exemplary substituted ketal phenazine Compound (I) of FIG. 3A and
the Comparative Example 2A includes the Comparative Compound (I) of
Example 1. Both devices utilized a viologen cathodic component. The
electrochemical cell set-up was similar to that described above for
Example 1.
[0080] Example 2A ("Ex. 2A") and Comparative Example 2A ("Comp. Ex.
2A") demonstrate the ability of the ketal phenazines of the present
disclosure to be used in an electrochromic device with a cathodic
component and exhibit a maximum absorbance when activated that is
red-shifted from a conventional anodic phenazine compound, such as
Comparative Compound (I).
Example 4
[0081] FIG. 7 is a plot of CIE LAB color space color values a* and
b* for exemplary examples Example 3A ("Ex. 3A") and Example 3B
("Ex. 3B") and a comparative example, Comparative Example 3A
("Comp. Ex. 3A"). Examples 3A and 3B and Comparative Example 3A
were tested using the same electrochromic device structure and the
same cathodic component. Examples 3A and 3B included the exemplary
substituted ketal phenazine Compound (I) of FIG. 3A in 20% by mole
diquatdiol and 30% by mole diquatdiol, respectively. Comparative
Example 3A included the comparative anodic component, Comparative
Compound (I) of Example 1. The electrochemical cell set-up was
similar to that described above for Example 1.
[0082] The voltage applied to the test devices for Examples 3A and
3B and Comparative Example 3A was stepped from 0 volts to 0.8 volts
and held at 0.8 volts for 5 min. The color space color values a*
and b* were determined using a D65 illuminant and an AOI of 2
degrees. The plot for Comparative Example 3A (Comp. Ex. 3A) shows
that the observed color stays within the greenish-yellowish
quadrant of the color space, when activated. However, Examples 3A
and 3B (Ex. 3A and Ex. 3B) show an observed color that shifts into
the red-blue quadrant of the color space, when activated.
[0083] Additional aspects of the present disclosure include:
[0084] According to a first aspect of the present disclosure, an
electro-optic element, includes: a first substrate defining first
and second surfaces, wherein a first electrically conductive layer
is disposed on the second surface; a second substrate defining
third and fourth surfaces, wherein a second electrically conductive
layer is disposed on the third surface; and an electrochromic
medium disposed in a cavity between the first and second
substrates, the electrochromic medium including an anodic component
and a cathodic component; wherein at least the anodic component is
configured to reversibly attenuate transmittance of light having a
wavelength within a predetermined wavelength range when in an
electrochemically activated state; and wherein the anodic component
includes a compound of Formula (I):
##STR00006##
[0085] wherein R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.6,
R.sub.7, R.sub.8, R.sub.9, R.sub.11, and R.sub.12 are individually
a hydrogen, alkyl, substituted alkyl, straight chain alkyl,
branched alkyl, or cycloalkyl and R.sub.5 and R.sub.10 are
individually an alkyl, substituted alkyl, straight chain alkyl,
branched alkyl, or cycloalkyl.
[0086] According to the first aspect of the present disclosure, in
a second aspect, wherein one of: R.sub.5 and R.sub.10; R.sub.11 and
R.sub.12; or R.sub.5, R.sub.10, R.sub.11, and R.sub.12,
individually comprise an alkyl, substituted alkyl, straight chain
alkyl, branched alkyl, or cycloalkyl substituted with at least one
polymerizable functional group.
[0087] According to the second aspect of the present disclosure, in
a third aspect, wherein the polymerizable functional group includes
at least one group selected from a vinyl group, acrylate group,
methacrylate group, vinyl ether group, hydroxyl group, isocyanate
group, oxetane group, amine group, and epoxy group.
[0088] According to the first aspect of the present disclosure, in
a fourth aspect, wherein at least one of R.sub.2, R.sub.5, R.sub.7,
and R.sub.10 are free of beta hydrogens.
[0089] According to the fourth aspect of the present disclosure, in
a fifth aspect, wherein at least one of R.sub.2, R.sub.5, R.sub.7,
and R.sub.10 includes one of a neopentyl group and tertiary
alkyl.
[0090] According to the first aspect of the present disclosure, in
a sixth aspect, wherein the anodic component includes at least one
material selected from
4-(2-tert-butyl-2-1-{7-[2-tert-butyl-4-(4-hydroxylbutyl)-1,3-dioxolan-2-y-
l}-5,10-bis(2,2-dimethylpropyl)
phenazine-2-yl)-1,3-dioxolan-4-yl}butane-1-ol (Compound (I)) and
4-(2-tert-butyl-2-1-{7-[2-tert-butyl-4-(4-hydroxymethyl)-1,3-dioxolan-2-y-
l]-5,10-bis(2,2-dimethylpropyl) phenazine-2-yl}-1,3-dioxolan-4-yl)
methanol (Compound (II)):
##STR00007##
[0091] According to any one of the first to the fifth aspects of
the present disclosure, in a seventh aspect, wherein the anodic
component further includes at least one additional anodic compound,
and wherein: the compound of Formula (I) includes a maximum
absorption in a wavelength range of 400 nm to 550 nm, when in an
electrochemically activated state; and the at least one additional
anodic compound includes a maximum absorption in a wavelength range
of 400 nm to 550 nm, when in an electrochemically activated state;
wherein the maximum absorption of the compound of Formula (I) is
within .+-.50 nm of the maximum absorption of the at least one
additional anodic compound, when the compound of Formula (I) and
the at least one additional anodic compound are in an
electrochemically activated state.
[0092] According to the first seventh of the present disclosure, in
an eighth aspect, wherein the compound of Formula (I) includes an
oxidation potential and the at least one additional anodic compound
includes an oxidation potential, and wherein: the oxidation
potential of the compound of Formula (I) is within .+-.60
millivolts of the oxidation potential of the at least one
additional anodic compound.
[0093] According to the seventh aspect of the present disclosure,
in a ninth aspect, wherein the at least one additional anodic
compound includes at least one material selected from metallocenes,
5,10-dihydrophenazines, phenothiazines, phenoxazines, carbazoles,
triphenodithiazines, triphendioxazines, ferrocene, substituted
ferrocenes, substituted ferrocenyl salts, phenazine, substituted
phenazines, phenothiazine, substituted phenothiazines, including
substituted dithiazines, thianthrene and substituted thianthrenes,
di-tert-butyl-diethylferrocene, 5,10-dimethyl-5,10-dihydrophenazine
(DMP), 3,7,10-trimethylphenothiazine,
2,3,7,8-tetramethoxy-thianthrene, 10-methylphenothiazine,
tetramethylphenazine (TMP),
bis(butyltriethylammonium)-para-methoxytriphenodithiazine (TPDT),
3,10-dimethoxy-7,14-(triethylammoniumbutyl)-triphenodithazinebis(tetraflu-
oroborate), and combinations thereof.
[0094] According to any one of the first to the ninth aspects of
the present disclosure, in a tenth aspect, wherein the cathodic
component includes at least one material selected from a viologen,
low-dimerizing viologen, non-dimerizing viologen, substituted
viologen, di-acrylate viologen, cathodic di-vinyl viologen,
cathodic di-vinyl ether viologen, cathodic di-epoxy viologen,
cathodic di-oxetane viologen, cathodic di-hydroxy viologen, and
combinations thereof.
[0095] According to any one of the first to the tenth aspects of
the present disclosure, in an eleventh aspect, wherein the anodic
component is one of dissolved in a solvent, incorporated into a
gel, or incorporated into a polymeric film.
[0096] According to a twelfth aspect of the present disclosure, a
medium for an electro-optic element, includes: an anodic component
configured to reversibly attenuate transmittance of light having a
wavelength within a predetermined wavelength range when in an
electrochemically activated state, and wherein the anodic component
includes a compound of Formula (I):
##STR00008##
wherein R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.6, R.sub.7,
R.sub.8, R.sub.9, R.sub.11, and R.sub.12 are individually a
hydrogen, alkyl, substituted alkyl, straight chain alkyl, branched
alkyl, or cycloalkyl and R.sub.5 and R.sub.10 are individually an
alkyl, substituted alkyl, straight chain alkyl, branched alkyl, or
cycloalkyl.
[0097] According to twelfth of the present disclosure, in a
thirteenth aspect, wherein one of: R.sub.5 and R.sub.10; R.sub.11
and R.sub.12; or R.sub.5, R.sub.10, R.sub.11, and R.sub.12,
individually comprise an alkyl, a substituted alkyl, straight chain
alkyl, branched alkyl, or cycloalkyl substituted with at least one
polymerizable functional group.
[0098] According to the thirteenth aspect of the present
disclosure, in a fourteenth aspect, wherein the polymerizable
functional group includes at least one group selected from a vinyl
group, acrylate group, methacrylate group, vinyl ether group,
hydroxyl group, isocyanate group, oxetane group, amine group, and
epoxy group.
[0099] According to the twelfth of the present disclosure, in a
fifteenth aspect, wherein at least one of R.sub.2, R.sub.5,
R.sub.7, and R.sub.10 are free of beta hydrogens.
[0100] According to the fifteenth of the present disclosure, in a
sixteenth aspect, wherein at least one of R2, R.sub.5, R.sub.7, and
R.sub.10 includes one of a neopentyl group and tertiary alkyl.
[0101] According to the twelfth of the present disclosure, in a
seventeenth aspect, wherein the anodic component includes at least
one material selected from
4-(2-tert-butyl-2-1-{7-[2-tert-butyl-4-(4-hydroxylbutyl)-1,3-dioxolan-2-y-
l}-5,10-bis(2,2-dimethylpropyl)
phenazine-2-yl)-1,3-dioxolan-4-yl}butane-1-ol (Compound (I)) and
4-(2-tert-butyl-2-{7-[2-tert-butyl-4-(4-hydroxymethyl)-1,3-dioxolan-2-yl]-
-5,10-bis(2,2-dimethylpropyl) phenazine-2-yl}-1,3-dioxolan-4-yl)
methanol (Compound (II)):
##STR00009##
[0102] According to the twelfth of the present disclosure, in an
eighteenth aspect, wherein the anodic component further includes at
least one additional anodic compound, and wherein: the compound of
Formula (I) includes a maximum absorption in a wavelength range of
400 nm to 550 nm, when in an electrochemically activated state; and
the at least one additional anodic compound includes a maximum
absorption in a wavelength range of 400 nm to 550 nm, when in an
electrochemically activated state; wherein the maximum absorption
of the compound of Formula (I) is within .+-.50 nm of the maximum
absorption of the at least one additional anodic compound, when the
compound of Formula (I) and the additional anodic compound are in
an electrochemically activated state.
[0103] According to the eighteenth of the present disclosure, in a
nineteenth aspect, wherein the compound of Formula (I) includes an
oxidation potential and the at least one additional anodic compound
includes an oxidation potential, and wherein: the oxidation
potential of the compound of Formula (I) is within .+-.60
millivolts of the oxidation potential of the at least one
additional anodic compound.
[0104] According to the nineteenth of the present disclosure, in a
twentieth aspect, wherein the at least one additional anodic
compound includes at least one material selected from metallocenes,
5,10-dihydrophenazines, phenothiazines, phenoxazines, carbazoles,
triphenodithiazines, triphendioxazines, ferrocene, substituted
ferrocenes, substituted ferrocenyl salts, phenazine, substituted
phenazines, phenothiazine, substituted phenothiazines, including
substituted dithiazines, thianthrene and substituted thianthrenes,
di-tert-butyl-diethylferrocene, 5,10-dimethyl-5,10-dihydrophenazine
(DMP), 3,7,10-trimethylphenothiazine,
2,3,7,8-tetramethoxy-thianthrene, 10-methylphenothiazine,
tetramethylphenazine (TMP),
bis(butyltriethylammonium)-para-methoxytriphenodithiazine (TPDT),
3,10-dimethoxy-7,14-(triethylammoniumbutyl)-triphenodithazinebis(tetraflu-
oroborate), and combinations thereof.
[0105] According to any one of the twelfth to the twentieth aspects
of the present disclosure, in a twenty-first aspect, wherein the
anodic component is one of dissolved in a solvent, incorporated
into a gel, or incorporated into a polymeric film.
[0106] It will be understood by one having ordinary skill in the
art that construction of the described disclosure and other
components is not limited to any specific material. Other exemplary
embodiments of the disclosure disclosed herein may be formed from a
wide variety of materials, unless described otherwise herein.
[0107] It is also important to note that the construction and
arrangement of the elements of the disclosure, as shown in the
exemplary embodiments, is illustrative only. Although only a few
embodiments of the present innovations have been described in
detail in this disclosure, those skilled in the art who review this
disclosure will readily appreciate that many modifications are
possible (e.g., variations in sizes, dimensions, structures, shapes
and proportions of the various elements, values of parameters,
mounting arrangements, use of materials, colors, orientations,
etc.) without materially departing from the novel teachings and
advantages of the subject matter recited. For example, elements
shown as integrally formed may be constructed of multiple parts, or
elements shown as multiple parts may be integrally formed, the
operation of the interfaces may be reversed or otherwise varied,
the length or width of the structures and/or members or connector
or other elements of the system may be varied, the nature or number
of adjustment positions provided between the elements may be
varied. It should be noted that the elements and/or assemblies of
the system may be constructed from any of a wide variety of
materials that provide sufficient strength or durability, in any of
a wide variety of colors, textures, and combinations. Accordingly,
all such modifications are intended to be included within the scope
of the present innovations. Other substitutions, modifications,
changes, and omissions may be made in the design, operating
conditions, and arrangement of the desired and other exemplary
embodiments without departing from the spirit of the present
innovations.
[0108] It will be understood that any described processes or steps
within described processes may be combined with other disclosed
processes or steps to form structures within the scope of the
present disclosure. The exemplary structures and processes
disclosed herein are for illustrative purposes and are not to be
construed as limiting.
[0109] It is also to be understood that variations and
modifications can be made on the aforementioned structures and
methods without departing from the concepts of the present
disclosure, and further it is to be understood that such concepts
are intended to be covered by the following claims unless these
claims by their language expressly state otherwise.
* * * * *