Granted Patent B2

US 7,902,322 · App. 12/270,714 · Granted Mar 8, 2011

Abstract

Claims (95)

1. A nonlinear optical chromophore comprising:

the structure D-π-A;

wherein D is a donor, π is a π-bridge, and A is an acceptor; and

a substituent group covalently attached to at least one of D, π, or A, and including a substituent center atom directly bonded to at least three aryl groups;

wherein the substituent center atom lies between the D-π-A structure and the at least three aryl groups.

2. The nonlinear optical chromophore of claim 1 ; wherein the substituent center is a carbon atom, a silicon atom, or a metal atom.

3. The nonlinear optical chromophore of claim 1 ; wherein the substituent center is a carbon atom, a silicon atom, a tin atom, a sulfur atom, a nitrogen atom, or a phosphorous atom.

4. The nonlinear optical chromophore of claim 1 ; wherein the aryl groups independently at each position include at least one selected from the group consisting of a phenyl ring, a naphthyl ring, a biphenyl group, a pyridyl ring, a bipyridyl group, and an anthracenyl group.

5. A nonlinear optical chromophore comprising:

the structure D-π-A;

wherein D is a donor, π is a π-bridge, and A is an acceptor; and

a substituent group covalently attached to at least one of D, π, or A, and including a substituent center atom directly bonded to at least three aryl groups;

wherein the substituent group includes the structure:

wherein X is the substituent center;

wherein Ar 1 , Ar 2 , and Ar 3 are the aryl groups; and

wherein L is a covalent linker attached to D, π, or A.

6. The nonlinear optical chromophore of claim 5 , wherein: X is selected from the group consisting of C, Si, Sn, S, N, and P;

wherein Ar 3 , Ar 2 , and Ar 3 each independently include at least one selected from the group consisting of a phenyl ring, a naphthyl ring, a biphenyl group, a pyridyl ring, a bipyridyl group, and an anthracenyl group; and

wherein L includes the structure:

wherein R 1 independently at each occurrence is selected from the group consisting of an H, an alkyl group, and a halogen;

wherein Y 1 independently at each occurrence is selected from the group consisting of —C(R 1 ) 2 —, O, S, —N(R 1 )—, —N(R 1 )C(O)—, —(O) 2 —, —C 6 H 6 —, and —OC 6 H 6 —;

wherein n is 0-6; and

wherein m is 1-3.

7. The nonlinear optical chromophore of claim 6 , wherein: D includes the structure

π includes the structure

and A includes the structure

wherein R 1 independently at each occurrence is H, on aliphatic group including alkyl or alkoxyl, or an aryl group;

R 2 independently at each occurrence is an alkyl group or an aryl group;

Z is a single bond or —CH═CH—;

Y 2 independently at each occurrence is O, S, N(R 1 ), or —C(R 1 ) 2 —;

R 3 independently at each occurrence is a cyano group, a nitro group, an ester group, or a halogen; and

at least one instance of R 1 , R 2 , or R 3 includes the substituent group.

8. A nonlinear optical chromophore comprising:

the structure D-π-A;

wherein D is a donor, π is a π-bridge, and A is an acceptor; and

a substituent group covalently attached to at least one of D, π, or A, and including a substituent center atom directly bonded to at least three aryl groups;

wherein D is

wherein X is the substituent center;

wherein Ar 1 , Ar 2 , and Ar 3 are the aryl groups;

wherein p is 2-6; and

wherein m=1-3.

9. The nonlinear optical chromophore of claim 8 , wherein X is C or Si.

10. The nonlinear optical chromophore of claim 9 , wherein π is:

and A is:

wherein R 1 independently at each occurrence is an H, an alkyl group, or a halogen;

wherein Z is a single bond or —CH═CH—;

wherein Y 2 is O, S, or —C(R 1 ) 2 —;

wherein R 2 independently at each occurrence is an alkyl group or an aryl group; and

wherein m=1-3.

11. The nonlinear optical chromophore of claim 10 having the structure

12. A nonlinear optical chromophore, comprising:

the structure D-π-A;

wherein D is a donor, π is a π-bridge, and A is an acceptor, and

wherein at least one of D, π, or A is covalently attached to a substituent group including the structure

wherein X is C or Si;

wherein Y 3 is N or P; and

wherein Ar 1 , Ar 2 , and Ar 3 are aryl groups;

and wherein the substituent group is covalently attached to one nonlinear optical chromophore.

13. The nonlinear optical chromophore of claim 12 , wherein the aryl groups independently at each position include a phenyl ring, a naphthyl ring, a biphenyl group, a pyridyl ring, a bipyridyl group, or an anthracenyl group.

14. A nonlinear optical chromophore, comprising:

the structure D-π-A;

wherein D is a donor, π is a π-bridge, and A is an acceptor, and

wherein at least one of D, π, or A is covalently attached to a substituent group including the structure

wherein X is C or Si;

wherein Y 3 is N or P;

wherein Ar 1 , Ar 2 , and Ar 3 are aryl groups;

wherein D includes the structure:

wherein π includes the structure:

and wherein A includes the structure:

wherein R 2 independently at each occurrence is an alkyl group or an aryl group;

wherein Z is a single bond or —CH═CH—;

wherein Y 2 independently at each occurrence is O, S, N(R 1 ), or —C(R 1 ) 2 —;

wherein R 3 independently at each occurrence is a cyano group, a nitro group, an ester group, or a halogen; and

wherein at least one instance of R 1 , at least one instance of R 2 , or at least one instance of R 3 includes the substituent group.

15. An electro-optic composite comprising the nonlinear optical chromophore of claim 1 , wherein the composite has greater than 90% temporal stability at 85° C. after 100 hours.

16. An electro-optic device comprising:

the nonlinear optical chromophore of claim 1 .

17. The electro-optic device of claim 16 , wherein the electro-optic device includes a Mach-Zehnder interferometer, a Michelson interferometer, a micro-ring resonator, or a directional coupler.

18. An electro-optic polymer including a nonlinear optical chromophore of any one of claims 1 , 5 , 8 , 12 , and 14 ; and wherein the electro-optic polymer has greater temporal stability than when an alkyl group is substituted for the aryl group.

19. A method, comprising:

a) providing a polymer including a nonlinear optical chromophore of any one of claims 1 , 5 , 8 , 12 , and 14 ; and

b) poling the polymer to form an electro-optic polymer, wherein the electro-optic polymer has greater temporal stability than when an alkyl group is substituted for at least one aryl group.

20. The method of claim 19 , wherein the substituent center is substituted with at least three aryl groups; and

wherein the electro-optic polymer has greater temporal stability than when alkyl groups are substituted for the aryl groups.

21. The method of claim 20 , wherein the nonlinear optical chromophore includes the structure:

wherein X is the substituent center;

wherein Ar 1 , Ar 2 , and Ar 3 are the aryl groups; and

wherein L is a covalent linker attached to D, π, or A.

22. The method of claim 20 , wherein the polymer is a composite.

23. The method of claim 20 , wherein the aryl group is sterically larger than the alkyl group.

24. The method of claim 20 , wherein:

the polymer has a T g ;

wherein the T g of the polymer is within approximately 5° C. compared to when an alkyl group is substituted for the aryl group; and

wherein the temporal stability of the polymer is greater compared to when an alkyl group is substituted for the aryl group.

25. The nonlinear optical chromophore of claim 1 ; wherein the substituent center is a heteroatom.

Assignments (10)