Protic-soluble organic electrochromic compounds

1. An electrochromic medium comprising a cathodic material, an anodic material, and a liquid or gel that comprises a protic solvent; wherein the electrochromic medium comprises at least one of

a cathodic protic-soluble electrochromic material represented by Formula (I):

wherein

R 1 and R 2 are each independently —(CH 2 ) m —CO 2 − , —(CH n )—P(O)(OH)(O − ), —(CH 2 ) p —OP(O)(OH)(O − ), or —(CH 2 ) q —S(O) 2 O − ;

R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , and R 10 are each independently H, OH, O-alkyl, F, Cl, Br, I, CN, NO 2 , alkyl, or aryl;

n is 2, 3, 4, 5, 6, 7, 8, 9, or 10;

m, p, and q are each independently 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10;

a cathodic protic-soluble electrochromic material represented by Formula (II):

wherein

R 11 and R 12 are each independently an alkyl group substituted with a N + (R 21 ) 3 or P + (R 22 ) 3 ;

R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , and R 20 are each independently H, OH, O-alkyl, F, Cl, Br, I, CN, NO 2 , alkyl, or aryl;

R 21 and R 22 are independently at each occurrence be alkyl substituted with a carboxylate, phosphonate, phosphate, or sulfonate or phenyl substituted with a carboxylate, phosphonate, phosphate, or sulfonate; and

M 1 is independently at each occurrence an alkali metal, an alkali earth metal, or an ammonium compound;

an anodic protic-soluble electrochromic material of represented by Formula (III):

wherein

R 23 and R 28 are each independently alkyl or alkyl substituted with a carboxylate, phosphonate, phosphate, or sulfonate, provided that at least one is alkyl substituted with a carboxylate, phosphonate, phosphate, or sulfonate;

R 24 , R 25 , R 26 , R 27 , R 29 , R 30 , R 31 , and R 32 are each independently H or alkyl;

x is an integer corresponding to the number of carboxylate, phosphonate, phosphate, sulfonate groups; and

M 2 is independently at each occurrence an alkali metal, an alkali earth metal, or an ammonium compound; and

an anodic protic-soluble electrochromic material represented by Formula (V), (VI), or (VII)

wherein

E 1 , E 2 , E 3 , E 4 , and E 5 are each independently O, S, or NR 47 ;

R 38 , R 47 , R 65 , and R 66 are independently at each occurrence an alkyl group substituted with a carboxylate, phosphonate, phosphate, or sulfonate;

R 39 , R 40 , R 41 , R 42 , R 43 , R 44 , R 45 , R 46 , R 48 , R 49 , R 50 , R 51 , R 52 , R 53 , R 54 , R 55 , R 56 , R 57 , R 58 , R 59 , R 60 , R 61 , R 62 , R 63 , R 67 , R 68 , R 69 , R 70 , R 71 , R 72 , R 73 , R 74 , R 75 , and R 76 are each independently H, F, Cl, Br, I, CN, OH, O-alkyl, SH, S-alkyl, NO 2 , alkyl, aryl, or amino, or any two adjacent groups of join to form a monocyclic, polycyclic, or heterocyclic group;

R 64 is alkylene;

y, y′, and y″ are each independently an integer corresponding to the number of carboxylate, phosphonate, phosphate, sulfonate groups; and

M 4 , M 5 , and M 6 are independently at each occurrence an alkali metal, an alkali earth metal, or an ammonium compound.

2. The electrochromic medium of claim 1 , wherein in Formula (II)

R 12 and R 21 are each independently —(CH 2 ) s —CO 2 − , —(CH 2 ) t —P(O)(OH)(O − ), —(CH 2 ) u —OP(O)(OH)(O − ), or —(CH 2 ) w —S(O) 2 O − ; and

s, t, u, and w are each independently 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10.

3. The electrochromic medium of claim 1 , wherein in Formula (III)

R 23 and R 28 are each independently alkyl, —(CH 2 ) m′ —CO 2 − , —(CH 2 ) n′ —P(O)(OH)(O − ), —(CH 2 ) p′ —OP(O)(OH)(O − ), or —(CH 2 ) q′ —S(O) 2 O − ; and

m′, n′, p′, and q′ are each independently 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10.

4. The electrochromic medium of claim 1 , wherein the cathodic protic-soluble electrochromic material of Formula (I) is

or a mixture thereof.

5. The electrochromic medium of claim 1 , wherein the anodic protic-soluble electrochromic material of Formula (III) is

6. The electrochromic medium of claim 1 , wherein the anodic protic-soluble electrochromic material of Formula (V) is

or a mixture thereof.

7. The electrochromic medium of claim 1 , wherein the protic solvent comprises an alcohol, a carboxylic acid, a primary amino compound, a secondary amino compound, water, or a mixture of any two or more thereof.

8. The electrochromic medium of claim 1 , wherein the protic solvent comprises methanol, ethanol, isopropanol, trifluoroethanol, butanol, ethylene glycol, propylene glycol, water, or a mixture of any two or more thereof.

9. The electrochromic medium of claim 1 , wherein the protic solvent comprises a diol.

10. The electrochromic medium of claim 1 , wherein the amount of protic solvent in the liquid or gel is from about 40 wt % to about 100 wt %.