U.S. patent application number 12/488962 was filed with the patent office on 2009-10-15 for electrochromic compounds.
This patent application is currently assigned to NTERA LIMITED. Invention is credited to David CORR, Mark KINSELLA, S. N. RAO, Niall STOBIE.
Application Number | 20090259042 12/488962 |
Document ID | / |
Family ID | 32605473 |
Filed Date | 2009-10-15 |
United States Patent
Application |
20090259042 |
Kind Code |
A1 |
CORR; David ; et
al. |
October 15, 2009 |
ELECTROCHROMIC COMPOUNDS
Abstract
The invention concerns electrochromic compounds of the general
formula I. These compounds may be used in electrochromic devices,
especially electrochromic devices comprising nanostructured
films.
Inventors: |
CORR; David; (Dublin 14,
IE) ; RAO; S. N.; (Dublin 14, IE) ; STOBIE;
Niall; (5 Dublin, IE) ; KINSELLA; Mark; (Co.
Dublin, IE) |
Correspondence
Address: |
MORGAN, LEWIS & BOCKIUS LLP
1701 MARKET STREET
PHILADELPHIA
PA
19103-2921
US
|
Assignee: |
NTERA LIMITED
County Dublin
IE
|
Family ID: |
32605473 |
Appl. No.: |
12/488962 |
Filed: |
June 22, 2009 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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10543588 |
Nov 2, 2005 |
7567371 |
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PCT/IE04/00015 |
Jan 30, 2004 |
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12488962 |
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Current U.S.
Class: |
546/22 |
Current CPC
Class: |
C09K 9/02 20130101; C07D
213/22 20130101 |
Class at
Publication: |
546/22 |
International
Class: |
C07F 9/38 20060101
C07F009/38 |
Foreign Application Data
Date |
Code |
Application Number |
Jan 31, 2003 |
EP |
03394012.3 |
Claims
1. A compound of the general formula I ##STR00010## wherein R.sup.1
is --(CH.sub.2).sub.m-- wherein m is zero or an integer from 1 to
10; or aryl or heteroaryl having up to 14 carbon atoms; or
branched-chain alkyl or alkenyl, or cycloalkyl, each having up to
10 carbon atoms; the aryl, heteroaryl, branched alkyl, branched
alkenyl or cycloalkyl radical optionally being attached to the
-P(O)(OH).sub.2 group via a --(CH.sub.2).sub.m-- linkage, wherein n
is zero or an integer from 1 to 10; it also being possible for the
and, heteroaryl, branched alkyl, branched alkenyl or cycloalkyl
radical to be optionally substituted by one or more of the
following substituenfs which may be the same or different: lower
alkyl, lower alkenyl, phenyl-lower alkyl, diphenyl-lower alkyl,
phenyl, phenoxy, lower alkanoyloxy, halogen, amino, cyano, nitro,
lower alkylamino, di-lower alkylamino, phenylamino, lower
alkanoylamino, benzoylamino; lower alkylsulfonylamino,
phenysulfonylamino, lower alkanoyl, benzoyl, carboxy, lower
alkoxycarbonyl carbamoyl, N-lower alkyl carbamoyl, N,N-di-lower
alkyl carbamoyl, ureido, N-lower alkylureido, lower alkylsulfonyl;
phenylsulfonyl; lower alkyl which is substituted by hydroxy; lower
alkoxy, amino, lower alkylamino, di-lower alkylamino, halogen,
carboxy or lower alkoxycarbonyl; lower alkoxy which is substituted
by hydroxy, lower alkoxy, amino, lower alkylamino, di-lower
alkylamino, halogen, carboxy or lower alkoxycarbonyl;
C.sub.3-C.sub.7-alkoxy; and/or bivalent methylenedioxy; it being
possible for all phenyl groups mentioned as such or in composed
radicals (such as benzoyl, phenylamino etc.) to be unsubstituted or
substituted by lower alkyl, lower alkoxy, halogen, hydroxy and/or
nitro; and R.sup.2 is R.sup.3R.sup.4 wherein R.sup.3 is
--(CH.sub.2).sub.p-- wherein p is zero or an integer from 1 to 10;
and R.sup.4 is --P(O)(OH).sub.2; or aryl or heteroaryl having up to
14 carbon atoms; or branched-chain alkyl or alkenyl, or cycloalkyl,
each having up to 10 carbon atoms, it being possible for the aryl,
heteroaryl, branched alkyl, branched alkenyl or cycloalkyl radical
to be unsubstituted or substituted by one or more of the
substituents given in the definition of R.sup.1; and X.sup.- is a
charge-balancing ion; with the provisos that R.sup.1 cannot be
--(CH.sub.2).sub.m-- wherein m is 2 or 3, when R.sup.2 is
--(CH.sub.2).sub.2----P(O)(OH).sub.2; and R.sup.1 cannot be
--(CH.sub.2).sub.m-- wherein m is 2, when R.sup.2 is phenyl.
2. A compound according to claim 1, wherein Rhub 1 is
--(CH.sub.2).sub.m-- wherein m is 1, 2 or 3; or phenyl which is
attached to the --P(O)(OH).sub.2 group via --(CH.sub.2).sub.n-- in
the para-position of the phenyl ring, wherein n is 1 or 2; R.sup.2
is R.sup.3R.sup.4 wherein R.sup.3 is --(CH.sub.2).sub.p-- wherein p
is zero, 1, 2or 3, and R.sup.4 is unsubstituted phenyl or naphthyl,
or phenyl or naphthyl which is mono-, di- or tri-substituted by
C.sub.1-4-alkyl, halogen, cyano, nitro, phenoxy or benzoyl; and
X.sup.- is Cl.sup.-, Br.sup.-, ClO.sub.4.sup.- PF.sub.6.sup.-,
BF.sub.4.sup.-; C.sub.2F.sub.6NO.sub.4S.sub.2.sup.- or
CF.sub.3SO.sub.3.sup.-, especially Cl.sup.- or PF.sub.6.sup.-.
3. A compound according to claim 1, wherein R.sup.1 is phenyl which
is attached to the --P(O)(OH).sub.2 group via --(CH.sub.2).sub.n--
in the para-position of the phenyl ring, wherein n is 1 or 2;
R.sup.2 is R.sup.3R.sup.4 wherein R.sup.3 is --(CH.sub.2).sub.p--
wherein p is zero, 1, 2 or 3 and R.sup.4 is -P(O) (OH).sub.2; arid
X.sup.- is Cl.sup.-, Br.sup.-, ClO.sub.4.sup.-, PF.sub.6.sup.-,
BF.sub.4.sup.-; C.sub.2F.sub.6NO.sub.4S.sub.2.sup.- or
CF.sub.3S.sub.3.sup.-, especially Cl.sup.- or PF.sub.6.sup.-.
4. A compound according to claim 1 selected from: (1)
1-Phosphonoethyl-1'-(3-propylphenyl)-4,4'-bipyridinium dichloride;
(2) 1-Phosphonoethyl-1'-(3-propylphenyl)-4,4'-bipyridinium
bis-hexafluorophosphate; (3)
1-Phosphonoethyl-1'-(2,4,6-trimethylphenyl)-4,4'-bipyridinium
dichloride; (4)
1-Phosphonoethyl-1'-(2,4,6-trimethylphenyl)-4,4'-bipyridimum
bis-hexafluorophosphate; (5)
1-Phosphonoethyl-1'-(naphthyl)-4,4'-bipyridinium dichloride; (6)
1-Phosphonoethyl-1'-(4-cyanonaphthyl)-4,4'-bipyridinium dichloride;
(7) 1-Phosphonoethyl-1'-(4-methylphenyl)-4,4'-bipyridinium
dichloride; (8)
1-Phosphonoethyl-1'-(4-cyanophenyl)-4,4'-bipyridinium dichloride;
(9) 1-Phosphonoethyl-1'-(4-fluorophenyl)-4,4'-bipyridinium
dichloride; (10)
1-Phosphonoethyl-1'-(4-phenoxyphenyl)-4,4'-bipyridinium dichloride;
(11) 1-Phosphonoethyl-1'-(4-t-butylphenyl)-4,4'-bipyridinium
dichloride; (12)
1-Phosphonoethyl-1'-(2,6-dimethylphenyl)-4,4'-bipyridinium
dichloride; (13)
1-Phosphonoethyl-1'-(3,5-dimethylphenyl)-4,4'-bipyridinium
dichloride; (14)
1-Phosphonoethyl-1'-(4-benzophenone)-4,4'-bipyridinium dichloride;
(15) 1-Phosphonobenzyl-1'-(3-propylphenyl)-4,4'-bipyridinium
dichloride; (16)
1-Phosphonobenzyl-1'-(3-propylphenyl)-4,4'-bipyridinium
bis-hexafluorophosphate; (17)
1-Phosphonobenzyl-1'-(phosphonoethyl)-4,4'-bipyridinium dichloride;
(18) 1-Phosphonobenzyl-1'-(2,4-dinitrophenyl)-4,4'-bipyridimum
dichloride; (19)
1-Phosphonobenzyl-1'-(2,4-dinitrophenyl)-4,4'-bipyridinium
bis-hexafluorophosphate; (20)
1-Phosphonobenzyl-1'-(4-phenoxyphenyl)-4,4'-bipyridinium
dichloride; (21)
1-Phosphonobenzyl-1'-(4-phenoxyphenyl)-4,4'-bipyridinium
bis-hexatluorophosphate; (22)
1-Phosphonobenzyl-1'-(4-fluorophenyl)-4,4'-bipyridinium dichloride;
(23) 1-Phosphonobenzyl-1'-(4-methylphenyl)-4,4'-bipyridinium
dichloride; (24)
1-Phosphonobenzyl-1'-(2,4,6-trimethylphenyl)-4,4'-bipyridiniurn
dichloride; (25) 1-Phosphonobenzyl-1'-(benzyl)-4,4'-bi pyridinium
dichloride; (26) 1-Phosphonobenzyl-1'-(naphthyl)-4,4'-bipyridiniuni
dichloride; (27) 1-Phosphonobenzyl-1'-(phenyl)-4,4'-bipyridinium
dichloride; (28)
1-Phosphonobenzyl-1'-(4-cyanophenyl)-4,4'-bipyridinium dichloride;
(29) 1-Phosphonobenzyl-1'-(4-benzophenone)-4,4'-bipyridinium
dichloride; (30)
1-Phosphonobenzyl-1'-(4-cyanonaphthyl)-4,4'-bipyridinium
dichloride; (31)
1-Phosphonobenzyl-1'-(2,6-dimethylphenyl)-4,4'-bipyridJnium
dichloride; (32)
1-Phosphonobenzyl-1'-(3,5-dimethylphenyl)-4,4'-bipyridinium
dichloride; and (33)
1-Phosphonoethyl-1'-(2,4,6-trimethylphenyl)-4,4'-bipyridinium
trifluoromethanesulfonimide.
5. A process for preparing a compound of the general formula I
given and defined in claim 1, which process comprises: (a) reacting
bipyridine of the formula II ##STR00011## with
1-halo-2,4-dinitrobenzene, if appropriate, to form a compound of
the formula III ##STR00012## (b) reacting the compound of formula
II or III with a phosphony Sating agent of the formula
R.sup.1-Y--P(O)(OR).sub.2 to form a compound of the formula IV
##STR00013## (c) reacting the compound of formula IV with
1-halo-2,4-dinitrobenzene, if appropriate, to form a compound of
the formula V ##STR00014## (d) reacting the compound of formula IV
or V with a compound of the formula R.sup.2-Y to form a compound of
the formula VI ##STR00015## (e) hydtolysing the compound of formula
VI to form a compound of the formula I'. ##STR00016## and if
appropriate, (f) converting the compound of formula I' to a
compound of the formula I ##STR00017## wherein in the above
formulae each R is an ester forming group which may be the same or
different, Y is halogen or amino, X'.sup.- is halogen, preferably
Br.sup.- or Cl.sup.-, and R.sup.1, R.sup.2 and X.sup.- are as
defined in claim 1.
6. A compound of the general formula V ##STR00018## wherein R.sup.1
is as defined in claim 1 except that the provisos of claim 1 are
excluded, each R is an ester forming group which may be the same or
different, and each X'.sup.- is independently halogen.
7. A compound according to claim 6, wherein each R is independently
methyl or ethyl; R.sup.1 is --(CH.sub.2).sub.m-- wherein m is 1, 2
or 3, or phenyl which is attached to the --P(O)(OH).sub.2 group via
--(CH.sub.2).sub.n-- in the para-position of the phenyl ring,
wherein n is 1 or 2; and each X'.sup.- is independently Br.sup.- or
Cl.sup.-.
8. A compound according to claim 6 which is
1-diethylbenzylphosphonate-1'-(2,4-dinitrophenyl)-4,4'-bipyridinium
dichloride.
9. An electrode or an electrochromic device comprising a compound
according to formula I. ##STR00019## wherein R.sup.1is an aryl
radical or a. heteroaryl radical having up to 14 carbon atoms; the
aryl radical or the heteroaryI radical optionally being attached to
the --P(O)(O).sub.2 group via a --(CH.sub.2).sub.n-- linkage,
wherein n is zero or an integer from 1 to 10; wherein the aryl
radical or the heteroaryl radical may be optionally substituted by
one or more of the foSloxving substituents which may be the same or
different; lower alkykl, lower alkenyl, phenyl-lower alkyl,
diphenyl-lower alkyl phenyl phenoxy, lower alkanoyloxy, halogen,
amino, eyano, nitro, lower alkylamino, di-lower alkylamino.
phenylamino, lower alkanoylamino, benzoylamino; lower
alkylsulfonylamino, phenysulfonylamino, lower alkanoyl, benzoyl
carboxy, lower alkoxycarbonyl, carbamoyl, N-lower alkylcarbamoyl,
N,N-di-lower alkylcarbamoyl, ureido, N-lower alkylureido, lower
alkylsulfonyl; phenylsulfonyl; lower alkyl which is substituted by
hydroxy, lower alkoxy, amino, lower alkylamino, di-lower alkyl
amino, halogen, carboxy or lower alkoxycarbonyl, lower alkoxy which
is substituted by hydroxy, lower alkoxy, amino, lower alkylamino,
di-lower alkylamino, halogen, carboxy or lower alkoxycarbonyl;
C.sub.3-C.sub.7-alkoxy; and/or bivalent methylenedioxy; wherein all
phenyl groups mentioned as such or in composed radicals (such as
benzoyl phenylamino etc.) may be unsubstituted or substituted by
lower alkyl, lower alkoxy, halogen, hydroxy and/or nitro; and
R.sup.2 is R.sup.3R.sup.4 wherein R.sup.3 is --(CH.sub.2).sub.p--
wherein p is zero or an integer from 1 to 10; and R.sup.4 is
--P(O)(OH).sub.2; or an aryl radical or a heteroaryl radical having
up to 14 carbon atoms; or branched-chain alkyl or alkenyl or
cycloalkyl each having up to 10 carbon atoms, it being possible for
the aryl, heteroaryl, branched alkyl, branched alkenyl or
cycloalkyl radicals to be unsubstituted or substituted by one or
more of the substituents given in the definition of R.sup.1; and
X.sup.- is a charge-balancing ion.
10. Use of a compound according to claim 1 in the manufacture of an
electrode or an electrochromic device.
11. An electrode or an electrochromic device comprising a compound
according to claim 6.
12. Use of a compound according to claim 6 in the manufacture of an
electrode or an electrochromic device.
Description
FIELD OF THE INVENTION
[0001] This invention relates to novel electrochromic compounds.
These compounds are useful in electrochromic devices such as
electric windows, displays and other optical devices that can
change colour according to the needs of the user. In particular,
the compounds may be used in electrochromic devices comprising
nanostructured films.
BACKGROUND
[0002] Viologen compounds, i.e. compounds which have a dipyridinium
group and are capable of reversible reduction/colouration, are
widely used in electrochromic devices. However, in conventional
viologen-based systems, diners may be formed due to the parallel
overlap of viologens, thereby preventing efficient decolouration in
the electrochromic device.
SUMMARY OF THE INVENTION
[0003] It is an object of the invention to avoid or minimise the
disadvantages of the prior art.
[0004] According to the present invention there are provided
compounds of the general formula I
##STR00001##
R.sup.1 is --(CH.sub.2).sub.m--wherein m is zero or an integer from
1 to 10; or aryl or heteroarl having up to 14 carbon atoms; or
branched-chain alkyl or alkenyl, or cycloalkyl, each having up to
10 carbon atoms; the aryl, heteroaryl, branched alkyl branched
alkenyl or cycloalkyl radical optionally being attached to the
--P(O)(OH).sub.2 group via a --(C.sub.2).sub.n-linkage, wherein n
is zero or an integer from 1 to 10; it also being possible for the
aryl, heteroaryl, branched alkyl, branched alkenyl or cycloalkyl
radical to be optionally substituted by one or more of the
following substituents which may be the same or different lower
alkyl, lower alkenyl, phenyl-lower alkyl, diphenyl-lower alkyl,
phenyl, phenoxy, lower alkanoyloxy, halogen, amino, cyano, nitro,
lower alkylamino, di-lower alkylamino, phenylamino, lower
alkanoylamino, benzoylamino; lower alkylsulfonylamino,
phenysulfonylamino, lower alkanoyl, benzoyl, carboxy, lower
alkoxycarbonyl, carbamoyl, N-lower alkylcarbamoyl, N,N-di-lower
alkylcarbamoyl, ureido, N-lower alkylureido, lower alkylsulfonyl;
phenyl sulfonyl; lower alkyl which is substituted by hydroxy, lower
alkoxy, amino, lower alkylamino, di-lower alkylamino, halogen,
carboxy or lower alkoxycarbonyl; lower alkoxy which is substituted
by hydroxy, lower alkoxy, amino, lower alkylamino, di-lower
alkylamino, halogen, carboxy or lower alkoxycarbonyl;
C.sub.3-C.sub.7-alkoxy; and/or bivalent methylenedioxy; it being
possible for all phenyl groups mentioned as such or in composed
radicals (such as benzoyl, phenylamino etc.) to be unsubstituted or
substituted by lower alkyl, lower alkoxy, halogen, hydroxy and/or
nitro; and R.sup.2 is R.sup.3R.sup.4 wherein R.sup.3 is
--(CH.sub.2).sub.p--wherein p is zero or an integer from 1 to 10;
and R.sup.4 is -P(O) (OH).sub.2; or aryl or heteroaryl having up to
14 carbon atoms; or branched-chain alkyl or alkenyl, or cycloalkyl,
each having up to 10 carbon atoms, it being possible for the aryl,
heteroaryl, branched alkyl, branched alkenyl or cycloalkyl radical
to be unsubstituted or substituted by one or more of the
substituents given in the definition of R.sup.1; and X is a
charge-balancing ion; with the provisos that R.sup.1 cannot be
--(CH.sub.2).sub.m-- wherein m is 2 or 3, when R.sup.2 is
--(CH.sub.2).sub.2--P(O)(OH).sub.2; and R.sup.1 cannot be
--(CH.sub.2).sub.m-- wherein m is 2, when R.sup.2 is phenyl.
[0005] The invention also provides processes for the manufacture of
the compounds of formula I, electrochromic devices comprising said
compounds, and their use in the manufacture of electrochromic
devices.
[0006] The invention further provides intermediate compounds which
are useful in the preparation of the compounds of formula I, said
intermediate compounds having the general formula V
##STR00002##
wherein R.sup.1 is as defined in formula I except that the provisos
are excluded, each R is an ester forming group which may be the
same or different, and each X'.sup.31 is independently halogen. The
compounds of formula V have electrochromic properties and may be
used in electrochromic devices.
[0007] The general definitions used herein have the following
meanings within the scope of the present invention.
[0008] The term "lower" means that groups so defined have
preferably up to and including 7, especially up to and including 4,
carbon atoms.
[0009] Lower alkyl as such or in composed radicals such as lower
alkoxy etc. is e.g. n-propyl, isopropyl, n-butyl, isobutyl,
sec.-butyl, tert.-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl,
isohexyl or n-heptyl, preferably ethyl and especially methyl.
[0010] Lower alkyl substituted by halogen is preferably
trifluoromethyl.
[0011] Lower alkanoyl as such or in composed radicals such as lower
alkanoyloxy etc. is e.g. formyl, acetyl, propionyl, n-butyryl,
pivaloyl or valeroyl,
[0012] Halogen is preferably chloro or fluoro, but may also be
bromo or iodo.
[0013] Phenylsulfonylamino means the radical
--NHSO.sub.2C.sub.6H.sub.5, lower alkylsulfonyl is --SO.sub.2-lower
alkyl.
[0014] Ureido and lower alkylureido represent the radicals
--NH--CONH.sub.2 and --NH--CONHAlk (3-alkylureido) or
-NAlk-CONH.sub.2 (1-alkylureido) respectively, wherein Alk is lower
alkyl.
[0015] In lower alkoxy radicals which are substituted by hydroxy,
epoxy, lower alkoxy, amino, lower alkylamino, di-lower alkylamino
or halogen, the substituents mentioned are normally separated from
the oxy group in lower alkoxy by at least two carbon atoms.
[0016] Suitable aryl groups include anthryl, phenanthryl, phenyl
and naphthyl. Phenyl and naphthyl are preferred.
[0017] Heteroaryl groups may have up to 4 heteroatoms which may be
the same or different selected from O, N and S. Suitable heteroaryl
groups include benzofuranyl, pyrrolyl, imidazolyl, pyrazolyl,
isothiazolyl, isoxazolyl, pyridyl, pyrazinyl, pyrimidinyl,
pyridazinyl, indolizinyl, indazolyl, purinyl, quinolyl,
naphthyridinyl, quinoxalinyl or phenoxazinyl.
[0018] Compounds of formula I are preferred in which R.sup.1 is
--(CH.sub.2).sub.m-- wherein m is 1, 2 or 3; or phenyl which is
attached to the --P(O)(OH).sub.2 group via --(CH.sub.2(.sub.n-- in
the para-position of the phenyl ring, wherein n is 1 or 2; R.sup.2
is R.sup.3R.sup.4 wherein R.sup.3 is --(CH.sub.2).sub.p-- wherein p
is zero, 1, 2 or 3, and R.sup.4 is unsubstituted phenyl or
naphthyl, or phenyl or naphthyl which is mono-, di- or
tri-substituted by C1-4-alkyl, halogen, cyano, nitro, phenoxy or
benzoyl; and X.sup.- is Cl.sup.-, Br.sup.-,
ClO.sub.4.sup.-PF.sub.6.sup.-, BF.sub.4.sup.-,
C.sub.2F.sub.6NO.sub.4S.sub.2.sup.- or CF.sub.3SO.sub.3.sup.-,
especially Cl.sup.31 , or PF.sub.6.sup.-.
[0019] Also preferred are compounds of formula I in which R1 is
phenyl which is attached to the --P(O)(OH).sub.2 group via
--(CH.sub.2).sub.n-- in the para-position of the phenyl ring,
wherein n is 1 or 2; R.sup.2 is R.sup.3R.sup.4 wherein R.sup.3 is
---(CH.sub.2).sub.p-- wherein p is zero, 1, 2 or 3 and R.sup.4 is
--P(O)(OH).sub.2; and X.sup.- is Cl.sup.-, Br.sup.-,
ClO.sub.4.sup.- PF.sub.6.sup.-, BF.sub.4.sup.-,
C.sub.2F.sub.6NO.sub.4S.sub.2.sup.- or CF.sub.3SO.sub.3.sup.-,
especially Cl.sup.- or PF.sub.6.sup.-.
[0020] Especially preferred are the following compounds of formula
I:
[0021] (1) 1-Phosphonoethyl-1'-(3-propylphenyl)-4,4'-bipyridinium
dichloride;
[0022] (2) 1-Phosphonoethyl-1'-(3-propylphenyl)-4,4'-bipyridinium
bis-hexafluorophosphate;
[0023] (3)
1-Phosphonoethyl-1'-(2,4,6-trimethylphenyl)-4,4'-bipyridinium
dichloride;
[0024] (4)
1-Phosphonoethyl-1'-(2,4,6-trimethylphenyl)-4,4'-bipyridinium
bis-hexafluorophosphate;
[0025] (5) 1-Phosphonoethyl-1'-(naphthyl)-4,4'-bipyridinium
dichloride;
[0026] (6) 1-Phosphonoethyl-1'-(4-cyanonaphthyl)-4,4'-bipyridnium
dichloride;
[0027] (7) 1-Phosphonoethyl-1'-(4-methylphenyl)-4,4'-bipyridinium
dichloride;
[0028] (8) 1-Phosphonoethyl-1'-(4-cyanophenyl)-4,4'-bipyridinium
dichloride;
[0029] (9) 1-Phosphonoethyl-1'-(4-fluorophenyl)-4,4'-bipyridinium
dichloride;
[0030] (10) 1-Phosphonoethyl-1'-(4-phenoxyphenyl)-4,4'-bipyridinium
dichloride;
[0031] (11) 1-Phosphonoethyl-1'-(4-t-butylphenyl)-4,4'-bipyridinium
dichloride;
[0032] (12)
1-Phosphonoethyl-1'-(2,6-dimethylphenyl)-4,4'-bipyridinium
dichloride;
[0033] (13)
1-Phosphonoethyl-1'-(3,5-dimethylphenyl)-4,4'-bipyridinium
dichloride;
[0034] (14) 1-Phosphonoethyl-1'-(4-benzophenone)-4,4'-bipyridinium
dichloride;
[0035] (15) 1-Phosphonobenzyl-1'-(3-propylphenyl)-4,4'-bipyridinium
dichloride;
[0036] (16) 1-Phosphonobenzyl-1'-(3-propylphenyl)-4,4'-bipyridinium
bis-hexafluorophosphate;
[0037] (17) 1-Phosphonobenzyl-1'-(phosphonoethyl)-4,4'-bipyridinium
dichloride;
[0038] (18)
1-Phosphonobenzyl-1'-(2,4-dinitrophenyl)-4,4'-bipyridinium
dichloride; (p (19)
1-Phosphonobenzyl-1'-(2,4-dinitrophenyl)-4,4'-bipyridinium
bis-hexafluorophosphate;
[0039] (20)
1-Phosphonobenzyl-1'-(4-phenoxyphenyl)-4,4'-bipyridinium
dichloride;
[0040] (21)
1-Phosphonobenzyl-1'-(4-phenoxyphenyl)-4,4'-bipyridinium
bis-hexafluorophosphate;
[0041] (22) 1-Phosphonobenzyl-1'-(4-fluorophenyl)-4,4'-bipyridinium
dichloride;
[0042] (23) 1-Phosphonobenzyl-1'-(4-methylphenyl)-4,4'-bipyridinium
dichloride;
[0043] (24)
1-Phosphonobenzyl-1'-(2,4,6-trimethylphenyl)-4,4'-bipyridinium
dichloride;
[0044] (25) 1-Phosphonobenzyl-4'-benzyl-4,4'-bipyridinium
dichloride,
[0045] (26) 1-Phosphonobenzyl-1'-naphthyl-4,4'-bipyridinium
dichloride;
[0046] (27) 1-Phosphonobenzyl-1'-phenyl-4'-bipyridinium
dichloride;
[0047] (28) 1-Phosphonobenzyl-1'-(4-cyanophenyl)-4,4'-bipyridimum
dichloride;
[0048] (29) 1-Phosphonobenzyl-1'-(4-benzophenone)-4,4'-bipyridinium
dichloride;
[0049] (30)
1-Phosphonobenzyl-1'-(4-cyanonaphthyl)-4,4'-bipyridinium
dichloride;
[0050] (31)
1-Phosphonobenzyl-1'-(2,6-dimethylphenyl)-4,4'-bipyridinium
dichloride;
[0051] (32)
1-Phosphonobenzyl-1'-(3,5-dimethylphenyl)-4,4'-bipyridinium
dichloride; arid
[0052] (33)
1-Phosphonoethyl-1'-(2,4,6-trimethylphenyl)-4,4'-bipyridinium
trifluoromethanesulfonimide.
[0053] Compounds of formula V are preferred in which each R is
independently methyl or ethyl; R.sup.1 is --(CH.sub.2).sub.m--
wherein m is 1, 2 or 3, or phenyl which is attached to the
--P(O)(OH).sub.2 group via --(CH.sub.2).sub.n-- in the
para-position of the phenyl ring, wherein n is 1 or 2, and each X'
is independently Br.sup.- or Cl.sup.-.
[0054] A preferred compound of formula V is 1
-diethylbenzylphosphonate-1'-(2,4-dinitrophenyl)-4,4'-bipyridinium
dichloride.
[0055] The compounds of formula I may be prepared by
(a) reacting bipyridine of the formula II
##STR00003##
with 1-halo-2,4-dinitrobenzene, if appropriate, to form a compound
of the formula III
##STR00004##
(b) reacting the compound of formula II or III with a
phosphonylating agent of the formula R.sup.1--Y--P(O)(OR).sub.2 to
form a compound of the formula IV
##STR00005##
(c) reacting the compound of formula IV with
1-halo-2,4-dinitrobenzene, if appropriate, to form a compound of
the formula V
##STR00006##
(d) reacting the compound of formula IV or V with a compound of the
formula R2-Y to form a compound of the formula VI
##STR00007##
(e) hydroiysing the compound of formula VI to form a compound of
the formula I',
##STR00008##
and if appropriate, (f) converting the compound of formula Y to a
compound of the formula I
##STR00009##
wherein in the above formulae each R is an ester forming group
which may be the same or different, Y is halogen or amino, X'.sup.-
is halogen, preferably Br.sup.- or Cl.sup.-, and R, R.sup.2 and
X.sup.- are as already defined.
[0056] Step (a) of the above process is only carried out when
compounds of the formula I are required wherein R1 is other than
--(CH.sub.2).sub.m--, and step (c) is only carried out when R.sup.2
in the formula I compounds is other than
--(CH.sub.2).sub.p--P(O)(OH).sub.2. The 1-halo-2,4-dinitrobenzene
used in steps (a) and (c) is preferably
1-chloro-2,4-dinitrobenzene.
[0057] Phospbonylating agents used in step (b) are preferably
dialkylhaloalkylphosphonates, such as diethylbromoethylphosphonate,
and dialkyl-4-amino aryl or substituted aryl phosphonates, such as
diethyl-4-aminobenzyl phosphonate or diethyl-4-aminonaphthyl
phosphonate.
[0058] Suitable reagents of the formula R.sup.2-Y used in step (d)
include liaioalkyibenzenes, such as bromopropylbenzene. and aniline
or substituted anilines.
[0059] The reactions steps (a)-(d) are generally carried out at
refluxing temperature in a suitable solvent. Preferred solvents
include toluene, acetonitrile and ethanol.
[0060] Hydrolysis step (e) is typically carried out in an solution
of hydrochloric acid or hydrobromic acid.
[0061] Step (f) is carried out when a compound of formula I is
required wherein X.sup.- is other that Br.sup.- or Cl.sup.-. The
conversion of X' to X'' is effected by reacting a compound of
formula I' with a salt of the desired balancing ion in aqueous
solution. Conversion of X' to X'' can confer greater stability and
greater solubility of the chromophore in a wider range of solvents,
resulting in the use of less concentrated solutions in
electrochromic devices with consequent reduction in costs.
[0062] The compounds of formula I improve the performance of
electrochromic devices, in particular those comprising
nanosfructured films. The compounds of formula I can provide
multiple colours, with enhanced stability for green colours, which
has not previously been achieved.
[0063] The invention is illustrated in the following Examples.
EXAMPLE 1
Synthesis of
1--Phosphonoethyl-1'-(3-propylphenyl)-4,4'-bipyridinium dichloride
(Compound 1)
(i) Synthesis of 1-Diethyl ethylphosphonate-4,4'-bipyridinium
bromide
[0064] 4,4'-Bipyridine (100 g, 0.64 moles) and diethyl
bromoethyiphosphonate (157 g, 0.64moles) in toluene (500 ml) in a 1
L round bottomed flask was refluxed until the solid precipitate of
the monocation salt was formed. The precipitate was filtered hot.
The filtrate was refluxed again and the process repeated until no
more solid formed. A yield of 95 g of the monocation was
obtained.
(ii) Synthesis of 1-Diethyl
ethylphosphonate-1'-(3-propylphenyl)-4,4'-bipyridinium
dibromide
[0065] 1-Diethyl ethylphosphonate-4,4'-bipyridinium bromide (0.005
moles) was added to 1-bromo-3-phenylpropane (0.075 moles) irs
acetonitrile (60 ml) and refluxed under stirring for twenty-four
hours. The resulting precipitate was filtered, washed with hot
acetonitrile and dried under vacuum to yield 1-diethyl
ethylphosphonate-1'-(3-propylphenyl)-4,4'-bipyridinium
dibromide.
(iii) Synthesis of
1-Phosphonoethyl-1'-(3-propylphenyl)-4,4'-bipyridinium
dichloride
[0066] 1-Diethyl
ethylphosphonate-1-(3-propylphenyl)-4,4'-bipyridinium dibromide was
added to a 50% hydrochloric acid solution (60 ml) and allowed to
reflux for twenty-four hours under stirring. The solvent was
removed under vacuum and the compound was crystallised by the
addition of ethanol, filtered and vacuum dried to yield
1-phosphonoethyl-1'-(3-propylphenyl)-4,4'-bipyridimum dichloride.
This compound is purple in the reduced state.
[0067] .sup.1H NM:R (CD.sub.3CN): .delta. 2.33-2.46(m, 4H),
2.81-2.83(m, 2H), 4.6-4.71 (d, 2H), 4.74-4.93(m, 2H), 7.23-7.37(ms
5H), 8.44-9.3(m, 8H).
EXAMPLE 2
Synthesis of 1-Phosphonoethyl-1'-(3-propylphenyl)-4,4'-bipyridinium
bis-hexafluorophosphate (Compound 2)
[0068] A solution of ammonium hexafluorophosphate (5 g) in water
(20 ml) was added to a cold solution of
1-phosphonoethyl-1'-(3-propylphenyl)-4,4'-bipyridinium dichloride
(2 g) prepared in Example 1 in water (20 ml), A precipitate of 1
-phosphonoethyl-1'-(2,4,6-trimethylphenyl)-4,4'-bipyridinium
bis-hexafluorophosphate (3 g) formed immediately and was filtered,
washed with cold water and dried.
EXAMPLE 3
Synthesis of
1-Phosphonoethyl-1'-(2,4,6-trimethylphenyl)-4,4'-bipyridinium
dichloride (Compound 3)
(i) Synthesis of 1-(Diethyl ethylphosphonate)-4,4'-bipyridinium
bromide
[0069] 4,4'-Bipyridine (100 g, 0.64 moles) and diethyl
bromoethylphosphonate (157 g, 0.64 moles) in toluene (500 ml) in a
1 L round bottomed flask was refluxed until the solid precipitate
of the monocation salt was formed. The precipitate was filtered
hot. The filtrate was refluxed again and the process repeated until
no more solid formed. A yield of 95 g of the monocation was
obtained.
(ii) Synthesis of 1-Diethyl
ethylphosphonate-1'-(2,4-dinitrophenyl)-4,4'-bipyridinium
monobromide monochloride
[0070] 1-Diethyl ethylphosphonate-4,4'-bipyridinium monobromide (50
g, 0.12 moles) was added to acetonitrile (400 ml) in a 1 L
round-bottomed flask and refluxed for thirty minutes. The clear
solution was decanted into a 1 L round-bottomed flask and
2,4-dinitrochlorobenzene (150 g, 0.74 moles) was added and refluxed
for eighteen hours. The precipitate formed was filtered and
digested with hot acetonitrile, filtered and dried under vacuum to
yield 50 g of 1-diethyl
ethylphosphonate-1'-(2,4-dinitrophenyl)-4,4'-bipyridinium
monobromide monochloride.
(iii) Synthesis of the 1-diethyl
ethylphosphonate-1'-(2,4,6-trimethylphenyl)-4,4'-bipyridinium
monobromide monochloride
[0071] 1-Diethyl
ethylphosphonate-1'-(2,4-dinitrophenyl)-4,4'-bipyridinium
monobromide monochloride (0.005 moles) was added to
2,4,6-trimethylaniltne (0.075 moles) in ethanol (60 ml) and
refluxed under stirring for 24 hrs. The ethanol was removed under
vacuum and water (80 ml) was added. The suspension was stirred and
filtered. The filtrate was decolourised with charcoal and the water
was removed under vacuum. The resulting product was digested in
acetonitrile, filtered and vacuum dried to yield the compound.
(iv) Synthesis of
1-phosphonoethyl-1'-(2,4,6-trimethylphenyl)-4,4'-bipyridinium
dichloride
[0072] 1-Diethyl
ethylphosphonate-1'-(2,4,6-trimethylphenyl)-4,4'-bipyridinium
monobromide monochloride was added to a 50% hydrochloric acid
solution (60 ml) and refluxed for twenty four hours. The solvent
was removed under vacuum and the compound was crystallised by the
addition of ethanol, filtered and vacuum dried to yield the
dichloride phosphonic acid derivative. This compound is blue in the
reduced state.
[0073] .sup.1H NMR (D.sub.2O): .delta. 1.91 (s, 6H), 2.24(s, 3H),
2.28-2.37(m, 2H), 4.76-4.85(m, 2H), 7.09(s, 2H), 8.46-9.1(m,
8H).
EXAMPLE 4
Synthesis of
1-phosphonoethyl-1'-(2,4,6-trimethylphenyl)-4,4'-bipyridinium
bis-hexafluorophosphate (Compound 4)
[0074] A solution of ammonium hexafluorophosphate (4.3 g) in water
(20 ml) was added to a solution of
1-phosphonoethyl-1'-(2,4,6-trimethylphenyl)-4,4'-bipyridinium
dichloride (2 g) prepared in Example 3 in water (20 ml). A
precipitate of
1-phosphonoethyl-1'-(2,4,6-trimethylphenyl)-4,4'-bipyridinium
bis-hexafluorophosphate (2.5 g) formed immediately and was filtered
and dried.
EXAMPLES 5-14
[0075] The procedure of Example 3 was repeated except that
2,4,6-trimethylaniline in step (iii) was replaced by the
substituted aniline indicated in Table I.
TABLE-US-00001 TABLE 1 Example No./ Compound Name/Colour Compound
No. in Reduced State Substituted Aniline .sup.1H NMR 5
1-Phosphonoethyl-1'- 1-Naphthylamine (D.sub.2O): .delta. 2.6-2.8(m,
(naphthyl)-4,4'- 2H), 4.8-4.95(m, 2H), bipyridinium dichloride
7.2-9.3 (m, 15H). (Green) 6 1-Phosphonoethyl-1'-(4-
4-Amino-1-naphthalene- (D.sub.2O): .delta. 2.23-
cyanonaphthyl)-4,4'- carbonitrile 2.34(m, 2H), 4.69- bipyridinium
dichloride 4.82(m, 2H), 8.12- (Green) 9.25(m, 14H), 7
1-Phosphonoethyl-1'-(4- 4-Methylaniline (D.sub.2O): .delta. 2.32(s,
3H); methylphenyl)-4,4'- 2.4-2.52(m, 2H); bipyridinium dichloride
4.75(m, 2H); 7.42(d, (Green) 2H); 7.53(d, 2H), 8.48-9.19(m, 8H). 8
1-Phosphonoethyl-1'-(4- 4-Cyanoaniline (D.sub.2O): .delta. 2.3(m,
2H), cyanophenyl)-4,4'- 4.8(m, 2H), 7.8(d, bipyridinium dichloride
2H), 8.l6(d, 2H), 8.4- (Green) 9.2(m, 8H). 9
1-Phosphonoethyl-1'-(4- 4-Fluoroaniline (D.sub.2O): .delta. 2.33(m,
fluorophenyl)-4,4'- 2H), 4.81(m, 2H), bipyridinium dichloride
7.35(d, 2H), 7.71(d, (Green) 2H), 8.58-9.22(m, 8H). 10
1-Phosphonoethyl-1'-(4- 4-Phenoxyaniline (CD.sub.3CN,PF.sub.6):
.delta. phenoxyphenyl)-4,4'- 2.36(m, 2H), 4.88(m, bipyridinium
dichloride 2H), 7.1-7.45(m, (Black) 5H), 7.44-7.74(m, 4H),
8.49-9.11 (m, 8H). 11 1-Phosphonoethyl-1'-(4- 4-tertButylaniline
(D.sub.2O): .delta.1.29(s, 9H), t-butylphenyl)-4,4'- 2.31(m, 2H),
4.78(m, bipyridinium dichloride 2H), 7.60(d, 2H,), (Green) 7.68(d,
2H), 8.56-9.2 (m, 8H). 12 1-Phosphonothyl-1'- 2,6-Dimethylaniline
(D.sub.2O): .delta. 2.03(s, 6H), (2,6-dimethylphenyl)- 2.4-2.51(m,
2H), 4,4'-bipyridinium 4,88-4.98 (m, 2H), dichloride (Blue)
7.4-7.6(m, 3H), 8.6- 9.2(m, 8H). 13 1-Phosphonoethyl-1'-
3,5-Dimethylaniline (D.sub.2O): .delta. 2.30(s, 6H),
(3.5-dimethylphenyl)- 2.35-2.43(m, 2H), 4,4'- bipyridinium 4.8(m,
2H), 7.28(s, dichloride (Green) 2H), 7.30(s, 1H), 8.4- 9.16(m, 8H),
14 1-Phosphonoethyl-1'-(4- 4-Aminobenzophenone (D.sub.2O): .delta.,
2.32(m, benzophenone)-4,4'- 2H), 4.8(m, 2H), 7.4- bipyridinium
dichloride 8.2(m, 9H), 8.40- (Green) 9.33(m, 8H).
EXAMPLE 15
Synthesis of
1--Phosphonobenzyl-1'-(3-propylphenyl)-4,4'-bipyridinium chloride
(Compound 15)
(i) Synthesis of 1-(2,4 Dinitrophenyi)-4,4'-bipyridinium
chloride
[0076] 4,4'-Bipyridine (10 g, 0.065 moles) and
chloro-2,4-dinitrobenzene (13 g, 0.065 moles) in ethanol (150 ml)
in a 250 ml flask were refluxed for fifteen hours and allowed to
cool. The ethanol was removed under vacuum and acetone (200 ml) was
added and the mixture was stirred. The suspension was filtered and
dried under vacuum to yield 1-(2,4-dinitrophenyl)-4,4'-bipyridinium
chloride (17.5 g).
(ii) Synthesis of 1-Diethyl benzylphosphonate-1'-bypyridinium
chloride
[0077] 1-(2,4-dinitrophenyl)-4,4'-bipyridinium chloride (7.3 g,
0.02 moles) and diethyl 4-aminobenzylphosphonate (5.5 g, 0.022
moles) in ethanol (150 ml) in a 250 ml flask were refluxed for six
hours and allowed to cool. The ethanol was removed under vacuum and
water (200 ml) was added and allowed to stir. The precipitate was
filtered and the filtrate was decolourised with charcoal. The water
was removed under vacuum to yield crude 1-diethyl
benzylphosphonate-4,4'-bypyridinium chloride (8 g).
(iii) Synthesis of 1-Diethyl
benzylphosphonate-1'-(3-propyiphenyl)-4,4'-bipyridinium
dichloride
[0078] 1-diethyl benzylphosphonate-4,1'-bypyridinium chloride (5 g,
0.0095 moles) was added to acetonitrile (100 ml) m a 250 ml flask
and refluxed for thirty minutes. The supernatant solution was
decanted into a 250 ml flask and 1-bromo-3-phenylpropane (3.8 g,
0.018 moles) was added and refluxed for forty-eight hours. The
precipitate formed was filtered and digested with hot acetonitrile,
filtered and dried under vacuum to yield 1-diethyl
benzylphosphonate-1'-(3-propylphenyl)-4,4'-bipyridinium dichloride
(4 g).
(iv) Synthesis of
1-Phosphonobenzyl-1'-(3-propylphenyl)-4,4'-bipyridinium
dichloride
[0079] 1-Diethyl benzylphosphonate-1'-(3-propylphenyl)-bipyridinium
dichloride (4 g) was added to a 50% Hydrochloric acid solution (60
ml) and allowed to reflux for twenty four hours under stirring. The
solvent was removed under vacuum and the compound was crystallised
by the addition of ethanol, filtered and vacuum dried to yield
1-phosphonobenzyl-1'-(3-propylphenyl)-4,4'-bipyridinium dichloride
(3.2 g). This compound is green in the reduced state.
[0080] .sup.1H NMR (CD3CN): .delta. 2.4 (m, 4H), 2.8 (m, 2H), 3.35
(d, 2H), 4.8 (m, 2H), 7.22 (m, 5H), 8.6-9.4 (m, 8H).
EXAMPLE 16
Synthesis of
1-Phosphonobenzyl-1'-(3-propylphenyl)-4,4'-bipyridinium
bis-hexafluorophosphate (Compound 1.6)
[0081] A solution of ammonium hexafluorophosphate (4 g) in water
(20 ml) was added to a solution of
1-phosphonobenzyl-1'-(3-propylphenyl)-4,4'-bipyridinium dichloride
(2 g) prepared in Example 15 in water (20 ml). A precipitate of
1-phosphonobenzy1'-(3-propylphenyl)-4,4'-bipyridinium
bis-hexafluorophosphate (2.2 g) formed immediately and was filtered
and dried.
EXAMPLE 17
Synthesis of
1-Phosphonobenzyl-1'-(phosphonoethyl)-4,4'-bipyridinium dichloride
(Compound 17)
(i) Synthesis of 1-(2,4 Dinitrophenyl)-4,4'-bipyridlnium
chloride
[0082] 4,4'-Bipyridine (10 g, 0.065 moles) and
chloro-2,4-dinitrobenzene (1.3 g, 0.065 moles) in ethanol (150 ml)
in a 250 ml flask were refluxed for fifteen hours and allowed to
cool. The ethanol was removed under vacuum and acetone (200 ml) was
added and the mixture was stirred. The suspension was filtered and
dried under vacuum to yield 1-(2,4-dinitrophenyl)-4,4'-bipyridinium
chloride (17.5 g).
(ii) Synthesis of 1-Diethyl benzylphosphonate-4,4'-bipyridinium
chloride
[0083] 1-(2,4-dinitrophenyl)-4,4'-bipyridinium chloride (7.3 g,
0.02 moles) and diethyl 4-aminobenzylphosphonate (5.5 g, 0.022
moles) in ethanol (150 ml) in a 250 ml flask were refluxed for six
hours and allowed to cool. The ethanol was removed under vacuum and
water (200 ml) was added and allowed to stir. The precipitate was
filtered and the filtrate was decolourised with charcoal. The water
was removed under vacuum to yield crude 1-diethyl
benzylphosphonate-4,4'-bipyridinium chloride (8 g).
(iii) Synthesis of 1-Diethyl benzylphosphonate-1'-diethyl ethyl
phosphonate-4,4'-bipyridimum dichloride
[0084] 1-diethyl benzylphosphonate-4,4'-bypyridinium chloride (5 g,
0.013 moles) was added to acetonitrile (100 ml) in a 250 ml flask,
and refluxed for thirty minutes. The supernatant solution was
decanted into a 250 ml flask and diethyl bromoethylphosphonate (6.3
g, 0.026 moles) was added and refluxed for forty-eight hours. The
precipitate formed was filtered and digested with hot acetonitrile,
filtered and dried under vacuum to yield 1-diethyl benzyl
phosphonate-1'-diethyl ethylphosphonate-4,4'-bipyridinium
dichloride (8 g).
(iv) Synthesis of
1-Phosphonobenzyl-1'-phosphonoethyl-4,4'-bipyridinium
dichloride
[0085] 1-Diethyl benzylphosphonate-1'-diethyl
ethylphosphonate-4,4'-bipyridinium dichloride (5g) was added to a
50% Hydrochloric acid solution (60 ml) and allowed to reflux for
twenty-four hours under stirring. The solvent was removed under
vacuum and the compound was crystallised by the addition of
ethanol, filtered and vacuum dried to yield
1-phosphonobenzyi-1'-phosphonoethyl-4,4'-bipyridinium dichloride
(3.6 g). This compound is green in the reduced state.
[0086] .sup.1H NMR (D2O); .delta. 2.4 (m, 2H), 3.32 (d, 2H), 4.85
(m, 2H), 7.8 (m, 4H), 8.6-9.2 (m, 8H).
EXAMPLE 18
Synthesis of
1-Phosphonobenzyl-1'-(2,4-dinitrophenyl)-4,4'-bipyridinium
dichloride (Compound 18)
(i) Synthesis of 1-(2,4 Dinitrophenyl)-4,4'-bipyridinium
chloride
[0087] 4,4'-Bipyridine (10 g, 0.065 moles) and
chloro-2,4-dinitrobenzene (13 g, 0.065 moles) in ethanol (150 ml)
in a 250 ml flask were refluxed for fifteen hours and allowed to
cool. The ethanol was removed under vacuum and acetone (200 ml) was
added and the mixture was stirred. The suspension was filtered and
dried under vacuum to yield 1-(2,4-dinitrophenyl)-4,4'-bipyridinium
chloride (17.5 g).
(ii) Synthesis of 1-Diethyl benzylphosphonate-4,4'-bypyridinium
chloride
[0088] 1-(2,4-dinitrophenyl)-4,4'-bipyridiniuni chloride (7.3 g,
0.02 moles) and diethyl 4-aminobenzylphosphonate (5.5 g. 0.022
moles) in ethanol (150 ml) in a 250 ml flask were refluxed for six
hours and allowed to cool. The ethanol was removed under vacuum and
water (200 ml) was added and allowed to stir. The precipitate was
filtered and the filtrate was decolourised with charcoal. The water
was removed under vacuum to yield crude 1-diethyl
benzylphosphonate-4,4'-bypyridinium chloride (8 g).
(iii) Synthesis of 1-Diethyl
benzylphosphonate-1'-(2,4-dinitrophenyl)-bipyridinium
dichloride
[0089] 1-diethyl benzylphosphonate-4,4'-bypyridinium chloride (5 g,
0.013 moles) was added to acetonitrile (100 ml) in a 250 ml flask,
and refluxed for thirty minutes. The supernatant solution was
decanted into a 250 ml flask and 2,4-dinitrochlorobenzene (10 g,
0.05 moles) was added and refluxed for forty-eight hours. The
precipitate formed was filtered and digested with hot acetonitrile,
filtered and dried under vacuum to yield 1-diethyl
benzylphosphonate-1'-(2,4-dinitrophenyl)-4,4'-bipyridinium
dichloride (6 g).
[0090] .sup.1H NMR (D20): .delta. 1.15 (6H), 3.42 (2H), 4.02 (4H),
7.57 (1H), 7.71 (1B), 8.18 (1H), 8.78 (4H), 9.31 (4H)
(iv) Synthesis of 1
-Phosphonobenzyl-1'-(2,4-dinitrophenyl)-4,4'-bipyridinium
dichloride
[0091] 1-Diethyl
benzylphosphonate-1'-(2,4-dinitrophenyl)-4,4'-bipyridinium
dichloride (5 g) was added to a 50% Hydrochloric acid solution (60
ml) and allowed to reflux for twenty-four hours under stirring. The
solvent was removed under vacuum and the compound was crystallised
by the addition of ethanol, filtered and vacuum dried to yield
1-phosphonobenxyl-1'-(2,4-dinitrophenyl)-4,4'-bipyridinium
dichloride (3.8 g). This compound is green in the reduced
state.
[0092] .sup.1H NMR (D2O): .delta. 2.45 (m, 2H), 4.85 (m, 2H), 8.2
(m, 2H), 8.45 (d, 1H), 8.8-9.4 (m, 8H).
EXAMPLE 19
Synthesis of
1-Phosphonobenzyl-1'-(2,4-dinitrophenyl)-4,4'-bipyridinium
bis-hexafluorophosphate (Compound 19)
[0093] A solution of ammonium hexafluorophosphate (4 g) in water
(20 ml) was added to a solution of
1-phosphonobenzyl-1'-(2,4-dinitrophenyl)-4,4'-bipyridinium
dichloride (2 g) prepared in Example 18 in water (20 ml). A
precipitate of
1-phosphonobenzyl-1'-(2,4-dinitrophenyl)-4,4'-bipyridinium
bis-hexafluorophosphate (2.8 g) formed immediately and was filtered
and dried.
EXAMPLE 20
Synthesis of
1-Phosphonobenzyl-1'-(4-phenoxyphenyl)-4,4'-bipyridinium dichloride
(Compound 20)
(i) Synthesis of 1-(2,4 Dinitrophenyl)-4,4'-bipyridinium
chloride
[0094] 4,4'-Bipyridine (10 g, 0.065 moles) and
chloro-2,4-dinitrobenzene (13 g, 0.065 moles) in ethanol (1.50 ml)
in a 250 ml flask, were refluxed for fifteen hours and allowed to
cool. The ethanol was removed under vacuum and acetone (200 ml) was
added and the mixture was stirred. The suspension was filtered and
dried under vacuum to yield 1-(2,4-dinhrophenyl)-4,4'-bipyridimum
chloride (17.5 g).
(ii) Synthesis of 1-Diethyl benzyiphosphonate-4,4'-bypyridinium
chloride
[0095] 1-(2,4-dinitrophenyl)-4,4'-bipyridinium chloride (7.3 g,
0.02 moles) and diethyl 4-aminobenzylphosphonate (5.5 g, 0.022
moles) in ethanol (150 ml) in a 250 ml flask were refluxed for six
hours and allowed to cool. The ethanol was removed under vacuum and
water (200 ml) was added and allowed to stir. The precipitate was
filtered and the filtrate was decolourised with charcoal. The water
was removed under vacuum to yield crude 1-diethyl
benzylphosphonat.e-4,4'-bipyridinium chloride (8 g).
(iii) Synthesis of 1-Diethyl
benzylphosphonate-1'-(2,4-dinitrophenyl)-4,4'-bipyridinium
dichloride
[0096] 1-diethyl benzylphosphonate-4,4'-bypyridinium chloride (5 g,
0.013 moles) was added to acetonitrile (100 ml) in a 250 ml flask
and refluxed for thirty minutes. The supernatant solution was
decanted into a 250 ml flask and 2,4-dinitrochlorobenzene (10 g,
0.05 moles) was added and refluxed for forty-eight hours. The
precipitate formed was filtered and digested with hot acetonitrile,
filtered and dried under vacuum to yield 1-diethyl
benzylphosphonate-1'-(2,4-dinitrophenyl)-4,4'-bipyridinium
dichloride (6 g).
(iv) Synthesis of 1-Diethyl
benzylphosphonate-1'-(4-phenoxyphenyl)-4,4'-bipyridinium
dichloride
[0097] 1-Diethyl
benzylphosphonate-1'-(2,4-dinitrophenyl)-bipyridinium dichloride (3
g, 0.005 moles) and 4-phenoxyaniline (1 g, 0.0055 moles) were
refluxed together in ethanol (60 ml) for twenty four hours. The
ethanol was removed under vacuum and water (80 ml) was added. The
suspension was stirred and filtered. The filtrate was decolourised
with charcoal and the water was removed under vacuum. The crude
product was digested in acetonitrile, filtered and vacuum dried to
yield 1-diethyl
benzylphosphonate-1'-(4-phenoxyphenyl)-4,4'-bipyridinium dichloride
(2 g).
(v) Synthesis of
1-Phosphonobenzyl-1'-(4-phenoxyphenyl)-4,4'-bipyridmium
dichloride
[0098] 1-Diethyl
benzylphosphonate-1'-(4-phenoxyphenyl)-bipyridinium dichloride (2
g) was added to a 50% Hydrochloric acid solution (60 ml) and
allowed to reflux for twenty four hours under stirring. The solvent
was removed under vacuum and the compound was crystallised by the
addition of ethanol, filtered and vacuum dried to yield
1-phosphonobenzy 1'-(4-phenoxy phenyl)-4,4-bipyridinium dichloride
(16 g).
[0099] .sup.1H NMR (D2O, dichloride): .delta. 3.16 (d, 2H),
6.95-7.8(m, 13H), 8.6-9.2 (m, 8H).
EXAMPLE 21
Synthesis of
1-Phosphonobenzyl-1'-(4-phenoxyphenyl)-4,4'-bipyridinium
bis-hexafluorophosphate (Compound 21)
[0100] A solution of ammonium hexafluorophosphate (2 g) in water
(20 ml) was added to a solution of
1-phosphonobenzyl-1'-(4-phenoxyphenyl)-4,4'-bipyridinium
di-chloride (1 g) prepared in Example 20 in water (20 ml). A
precipitate of
1-phosphonobenzyl-1'-(4-phenoxy-phenyl)-4,4'-bipyridinium
bis-hexafluorophosphate (1.4 g) formed immediately and was filtered
and dried.
EXAMPLES 22-24
[0101] The procedure of Example 20 was repeated except that the
4-phenoxyanline in step (iv) was replaced by the substituted
aniline indicated in Table 2.
TABLE-US-00002 TABLE 2 Example No./ Compound Name/Colour Compound
No. in Reduced State Substituted Aniline .sup.1HNMR 22
1-Phosphonobenzyl-1'-(4- 4-Fluoroaniline (D.sub.2O, dichloride):
fluorophenyl)-4,4'- .delta. 3.15(d, 2H), bipyridinium dichloride
7.1-7.7(m, 8H), (Green) 8.6-9.3(m, 8H) 23 1-Phosphonobenzyl-1'-(4-
4-Methylaniline (D.sub.2O, dichloride): .delta. methylphenyl)-4,4'-
2.33(s, 3H), 3.25(d, bipyridinium dichloride 2H), 7.35-7.8(m, 8H),
(Green) 8.7-9.3(m, 8H) 24 1-Phosphonobenzyl-1'- 2,4,6- (D.sub.2O,
dichloride): (2,4,6-trimethylphenyl)- Trimethylaniline .delta.
1.99(s, 9H), 3.18(d, 4,4'-bipyridinium dichloride. 2H), 7.12(s,
2H), 7.5- (Blue) 7.7(dd, 4H), 8.6-9.3 (m, 8H)
[0102] A fluorine doped tin oxide (FTO, 15 .OMEGA. per square)
coated glass substrate (20 mm.times.10 mm) was coated with
nanocrystalline titanium dioxide (20 mm.times.10 mm) by
screenprinting. The coating was heated in air at 450.degree. C. for
45 minutes to give a transparent nanostructured titanium dioxide
film.
[0103] The film was immersed in a solution of Compound 3, prepared
in Example 3, i.e.
1-phosphonoethyl-1'-(2,4,6-trimethylphenyl)-4,4'-bipyridinium
dichloride (0.001 M), in de-ionised water for 30 minutes. In this
way the chromophore was adsorbed to the nanostructured film. The
film was rinsed in ethanol for 15 minutes and air-dried. An
electrochemical cell was assembled using the prepared film as the
cathode. A silver/silver chloride electrode was used as the
reference electrode and a platinum wire as the counter electrode.
The three electrodes were immersed in a 0.2 M electrolyte solution
of lithium perchlorate in gamma butyrolactone that was purged with
nitrogen.
[0104] The electrodes were connected to a Solartron 1285
potentostat and a voltage sweep was performed from .+-.0.5V to
-1.1V at a scan rate of 50 mV/s. The cathodic reduction of the
adsorbed Compound 3 resulted in a blue colouration of the device.
As the voltage sweep continued and Compound 3 was oxidised, the
decolouration of Compound 3 was observed.
[0105] Electrodes comprising the compounds of Examples 5-14 were
prepared and tested according to the above procedure, and the
colour of each of the compounds in the reduced state is given in
Table 1.
EXAMPLE 26
[0106] Cathodic electrodes comprising the compounds of Examples 3
and 17 were prepared as in Example 25. These electrodes were sealed
to a second FTO (15 .OMEGA./square) coated glass substrate with an
epoxy glue and heated to 130.degree. C. for 1 hour to cure the
glue. The cells thus formed were filled under vacuum with an
electrolyte solution containing ferrocene (0.05 M) and lithium
perchlorate (0.2 M) in gamma butyrolactone and finally sealed with
a UV curable glue. Application of -1.3V across the resulting
electrochromic devices lead to uniform colouration and upon removal
of the voltage the devices returned to their clear state. UV/Vis
spectral measurements were made on a Shimadzu UV240IPC spectrometer
and transmission levels are reported at. 550 nm.
[0107] The data obtained are shown in Table 3 and indicate a
successful functioning of each device in that there is a
significant reduction in transmission in switching from the clear
to the coloured state.
TABLE-US-00003 TABLE 3 Device Compound of Transmission in
Transmission in No. Example No. Clear State Coloured State 1 3 72%
31% 2 17 75% 46%
EXAMPLE 27
[0108] A cathodic electrode was prepared as in Example 25 with the
exception that the film was immersed in an equimolar (0.00.1 M)
solution of two viologens,
1-phosphonoethyl-1'-(2,4,6-immethylphenyl)-4,4'-bipyridinium
dichloride (Compound 3 prepared in Example 3) and
1-phosphonobenzyl-1'-(phosphonoethyl)-4,4'-bipyridinium dichloride
(Compound 17 prepared in Example 17). The cathode was sealed to a
second substrate, filled and finally sealed according to Example
26.
[0109] Application of -1.3V across the resulting electrochromic
device lead to a uniform green/grey colouration and upon removal of
the voltage the device returned to its clear state. UV/Vis spectral
measurements were carried out as described in Example 26.
[0110] It can be observed that this device functions similarly to
those in Example 26. However, the colouration is different when two
viologens are used (i.e. green/grey) as compared with the previous
devices which only have one viologen.
TABLE-US-00004 TABLE 4 Device Compound of Transmission in
Transmission in No. Example No. (Clear State) Coloured State 1 3 +
17 82% 25%
EXAMPLE 28
[0111] Cathodic electrodes comprising the compounds of Examples 3,
7, 9, 10, 11, 13 and 17 were prepared as in Example 25. Anodes were
constructed from respective second FTO substrates (50 mm.times.50
mm). These substrates were coated with antimony doped tin oxide
(ATO) by screenprinting and heated at 60.degree. C. for 20-30
minutes. A white reflector paste comprising silica-coated titanium
dioxide was applied by screenprinting over each ATO layer and each
double layer was allowed to sinter at 450.degree. C. for 45
minutes. Each set of two electrodes was bonded together in a
sandwich configuration to form a cell. Each cell was filled with an
electrolyte solution of lithium trifluormethanesulfonimide (10 mM)
in gamma butyrolactone. The resulting devices were sealed and
initial reflectance measurements were made on an Ocean Optics
SD2000 spectrometer equipped with an integrating sphere.
[0112] Each device had a diffuse reflectance in the clear state of
36%. When a voltage of -1.3V was applied across each device, it
coloured and the reflectance value at 550 nm dropped to
approximately 2.5%. The ratio of the clear state reflectance to the
coloured state reflectance is a measure referred to as the contrast
ratio (CR). In each case, the contrast ratio was 36/2.5=14.4.
[0113] The stability of the devices prepared above was tested by
cycling them between the coloured and clear states many thousands
of times at a temperature of about 70.degree. C. The contrast ratio
(CR) was measured before and after cycling to assess the level of
degradation of the devices. The results are shown in Table 5.
TABLE-US-00005 Device Compound CR CR No. No. Number of Cycles
before after 1 3 1,000,000 14.4 1.3 2 7 50,000 14.4 14.4 3 9 50,000
14.4 14.4 4 10 50,000 14.4 14.4 5 11 50,000 14.4 14 6 13 50,000
14.4 14 7 17 200,00 14.4 14.4
[0114] The results show that degradation of the contrast ratio is
negligible even at 1.times.10.sup.6 cycles.
* * * * *