Design and synthesis of advanced NLO materials for electro-optic applications

A device comprising a thiophene-containing chromophore of the structure

• 93
• wherein, independently at each occurrence,
• D is selected from the group consisting of
• 94 95
• π1 and π2 are independently
• 96
• A is selected from the group consisting of
• 97
• X is O or S;
• R is alkyl, aryl or heteroalkyl;
• n is 1, 2, 3 or 4;
• R1 is hydrogen, alkyl, aryl or heteroalkyl;
• Y is O, S or Se;
• Z1 is O, S, Se, NR1, C(R1)2 or —C(R1)═C(R1)—;
• 98
• q is 0 or 1;
• p is 0, 1 or 2;
• o is 0, 1, or 2;
• and m is 2, 3 or 4.

A device comprising a thiophene-containing chromophore of the structure

• 101
• wherein, independently at each occurrence,
• R is alkyl, aryl or heteroalkyl;
• R1 is alkyl, aryl or heteroalkyl;
• and
• X is O or S.

A device comprising a thiophene-containing chromophore of the structure

• 102
• wherein, independently at each occurrence,
• R is alkyl, aryl or heteroalkyl;
• R1 is alkyl, aryl or heteroalkyl;
• and
• X is O or S.

A device comprising a thiophene-containing chromophore of the structure

• 103
• wherein, independently at each occurrence,
• D is an electron donating group having low electron affinity relative to the electron affinity of
• 104
• π is absent or a bridge that provides electronic conjugation between D and the double bond adjacent to π;
• and
• R is alkyl, aryl, heteroalkyl or heteroaryl.

A device comprising a composition of matter of the formula

• E—Lg
• wherein E is a chromophore;
• L comprises a chemically reactive group that is crosslinkable;
• and g=1-24, where the chromophore has the structure
• 107
• wherein, independently at each occurrence,
• D is an electron donating group having low electron affinity relative to the electron affinity of A;
• π1 is absent or a bridge that provides electronic conjugation between D and the thiophene ring;
• π2 is absent or a bridge that provides electronic conjugation between A and the thiophene ring;
• A is an electron accepting group having high electron affinity relative to the electron affinity of D;
• X is O or S;
• R is alkyl, aryl, heteroalkyl or heteroaryl;
• and
• n is 1, 2, 3 or 4.

A device comprising a composition of matter of the formula

• E—Lg
• wherein E is a chromophore;
• L comprises a chemically reactive group that is crosslinkable;
• and g=1-24, where the chromophore has the structure
• 108
• wherein, independently at each occurrence,
• D is an electron donating group having low electron affinity relative to the electron affinity of
• 109
• π is absent or a bridge that provides electronic conjugation between D and the double bond adjacent to π;
• and
• R is alkyl, aryl, heteroalkyl or heteroaryl.

A device comprising a composition of matter, the composition of matter comprising a chromophore non-covalently incorporated into a crosslinkable polymer matrix, wherein the chromophore has the structure

• 110
• wherein, independently at each occurrence,
• D is an electron donating group having low electron affinity relative to the electron affinity of A;
• π1 is absent or a bridge that provides electronic conjugation between D and the thiophene ring;
• π2 is absent or a bridge that provides electronic conjugation between A and the thiophene ring;
• A is an electron accepting group having high electron affinity relative to the electron affinity of D;
• X is O or S;
• R is alkyl, aryl, heteroalkyl or heteroaryl;
• and
• n is 1, 2, 3 or4.

A device comprising a composition of matter, the composition of matter comprising a chromophore non-covalently incorporated into a crosslinkable polymer matrix, wherein the chromophore has the structure

• 111
• wherein, independently at each occurrence,
• D is an electron donating group having low electron affinity relative to the electron affinity of
• 112
• π is absent or a bridge that provides electronic conjugation between D and the double bond adjacent to π;
• and
• R is alkyl, aryl, heteroalkyl or heteroaryl.

A process comprising sequentially 1) incorporating a chromophore into a polymer matrix;

• 2) maintaining the polymer matrix at a selected temperature to allow effective chromophore mobility;
• and 3) applying an electric field sufficient to induce dipole alignment of the chromophore in the polymer matrix, wherein the chromophore has the structure
• 113
• wherein, independently at each occurrence,
• D is an electron donating group having low electron affinity relative to the electron affinity of A;
• π1 is absent or a bridge that provides electronic conjugation between D and the thiophene ring;
• π2 is absent or a bridge that provides electronic conjugation between A and the thiophene ring;
• A is an electron accepting group having high electron affinity relative to the electron affinity of D;
• X is O or S;
• R is alkyl, aryl, heteroalkyl or heteroaryl;
• and
• n is 1, 2, 3 or 4.

A process comprising sequentially 1) incorporating a chromophore into a polymer matrix;

• 2) maintaining the polymer matrix at a selected temperature to allow effective chromophore mobility;
• and 3) applying an electric field sufficient to induce dipole alignment of the chromophore in the polymer matrix, wherein the chromophore has the structure
• 114
• wherein, independently at each occurrence,
• D is an electron donating group having low electron affinity relative to the electron affinity of
• 115
• π is absent or a bridge that provides electronic conjugation between D and the double bond adjacent to π;
• and
• R is alkyl, aryl, heteroalkyl or heteroaryl.

A process comprising 1) providing a composition of matter;

• 2) maintaining the composition at a selected temperature to allow effective chromophore mobility;
• and 3) applying an electric field sufficient to induce dipole alignment of the chromophores, wherein the composition of matter comprises a material of the formula
• E—Lg
• wherein E is a chromophore;
• L comprises a chemically reactive group that is crosslinkable;
• and g=1-24, and where the chromophore has the structure
• 116
• wherein, independently at each occurrence,
• D is an electron donating group having low electron affinity relative to the electron affinity of A;
• π1 is absent or a bridge that provides electronic conjugation between D and the thiophene ring;
• π2 is absent or a bridge that provides electronic conjugation between A and the thiophene ring;
• A is an electron accepting group having high electron affinity relative to the electron affinity of D;
• X is O or S;
• R is alkyl, aryl, heteroalkyl or heteroaryl;
• and
• n is 1, 2, 3 or 4.

A process comprising 1) providing a composition of matter;

• 2) maintaining the composition at a selected temperature to allow effective chromophore mobility;
• and 3) applying an electric field sufficient to induce dipole alignment of the chromophores, wherein the composition of matter comprises a material of the formula
• E—Lg
• wherein E is a chromophore;
• L comprises a chemically reactive group that is crosslinkable;
• and g=1-24, and where the chromophore has the structure
• 117
• wherein, independently at each occurrence,
• D is an electron donating group having low electron affinity relative to the electron affinity of
• 118
• π is absent or a bridge that provides electronic conjugation between D and the double bond adjacent to π;
• and
• R is alkyl, aryl, heteroalkyl or heteroaryl.

An interferometric optical modulator or switch, comprising:

• 1) an input waveguide;
• 2) an output waveguide;
• 3) a first leg having a first end and a second end, the first leg being coupled to the input waveguide at the first end and to the output waveguide at the second end;
• and 4) a second leg having a first end and a second end, the second leg being coupled to the input waveguide at the first end and to the output waveguide at the second end, wherein at least one of the first and second legs includes a composition of matter comprising a chromophore of the structure
• 119
• wherein, independently at each occurrence,
• D is an electron donating group having low electron affinity relative to the electron affinity of A;
• π1 is absent or a bridge that provides electronic conjugation between D and the thiophene ring;
• π2 is absent or a bridge that provides electronic conjugation between A and the thiophene ring;
• A is an electron accepting group having high electron affinity relative to the electron affinity of D;
• π2 is absent or a bridge that provides electronic conjugation between A and the thiophene ring;
• A is an electron accepting group having high electron affinity relative to the electron affinity of D;
• X is O or S;
• R is alkyl, aryl, heteroalkyl or heteroaryl;
• and
• n is 1, 2, 3 or 4.

An interferometric optical modulator or switch, comprising:

• 1) an input waveguide;
• 2) an output waveguide;
• 3) a first leg having a first end and a second end, the first leg being coupled to the input waveguide at the first end and to the output waveguide at the second end;
• and 4) a second leg having a first end and a second end, the second leg being coupled to the input waveguide at the first end and to the output waveguide at the second end, wherein at least one of the first and second legs includes a composition of matter comprising a chromophore of the structure
• 120
• wherein, independently at each occurrence,
• D is an electron donating group having low electron affinity relative to the electron affinity of
• 121
• π is absent or a bridge that provides electronic conjugation between D and the double bond adjacent to π;
• and
• R is alkyl, aryl, heteroalkyl or heteroaryl.

An interferometric optical modulator or switch, comprising:

• 1) an input waveguide;
• 2) an output waveguide;
• 3) a first leg having a first end and a second end, the first leg being coupled to the input waveguide at the first end and to the output waveguide at the second end;
• and 4) a second leg having a first end and a second end, the second leg being coupled to the input waveguide at the first end and to the output waveguide at the second end, wherein at least one of the first and second legs includes a composition of matter of the formula
• E—Lg
• wherein E is a chromophore;
• L comprises a chemically reactive group that is crosslinkable;
• and g=1-24, where the chromophore has the structure
• 122
• wherein, independently at each occurrence,
• D is an electron donating group having low electron affinity relative to the electron affinity of
• 123
• π is absent or a bridge that provides electronic conjugation between D and the double bond adjacent to π;
• and
• R is alkyl, aryl, heteroalkyl or heteroaryl.

An interferometric optical modulator or switch, comprising:

• 1) an input waveguide;
• 2) an output waveguide;
• 3) a first leg having a first end and a second end, the first leg being coupled to the input waveguide at the first end and to the output waveguide at the second end;
• and 4) a second leg having a first end and a second end, the second leg being coupled to the input waveguide at the first end and to the output waveguide at the second end, wherein at least one of the first and second legs includes a composition of matter of the formula
• E—Lg
• wherein E is a chromophore;
• L comprises a chemically reactive group that is crosslinkable;
• and g=1-24, where the chromophore has the structure
• 124
• wherein, independently at each occurrence,
• D is an electron donating group having low electron affinity relative to the electron affinity of
• 125
• π is absent or a bridge that provides electronic conjugation between D and the double bond adjacent to π;
• and
• R is alkyl, aryl, heteroalkyl or heteroaryl.

An optical router comprising a plurality of switches, wherein each switch comprises:

• 1) an input;
• 2) an output;
• 3) a first waveguide extending between the input and the output;
• and 4) a second waveguide aligned to the first waveguide and positioned for evanescent coupling to the first waveguide;
• wherein at least one of the first and second waveguides comprises a thiophene-containing chromophore of the structure
• 126
• wherein, independently at each occurrence,
• D is an electron donating group having low electron affinity relative to the electron affinity of A;
• π1 is absent or a bridge that provides electronic conjugation between D and the thiophene ring;
• π2 is absent or a bridge that provides electronic conjugation between A and the thiophene ring;
• A is an electron accepting group having high electron affinity relative to the electron affinity of D;
• X is O or S;
• R is alkyl, aryl, heteroalkyl or heteroaryl;
• and
• n is 1, 2, 3 or 4.

An optical router comprising a plurality of switches, wherein each switch comprises:

• 1) an input;
• 2) an output;
• 3) a first waveguide extending between the input and the output;
• and 4) a second waveguide aligned to the first waveguide and positioned for evanescent coupling to the first waveguide;
• wherein at least one of the first and second waveguides comprises a thiophene-containing chromophore of the structure
• 127
• wherein, independently at each occurrence,
• D is an electron donating group having low electron affinity relative to the electron affinity of
• 128
• π is absent or a bridge that provides electronic conjugation between D and the double bond adjacent to π;
• and
• R is alkyl, aryl, heteroalkyl or heteroaryl.

An optical router comprising a plurality of switches, wherein each switch comprises:

• 1) an input;
• 2) an output;
• 3) a first waveguide extending between the input and the output;
• and 4) a second waveguide aligned to the first waveguide and positioned for evanescent coupling to the first waveguide;
• wherein at least one of the first and second waveguides comprises a composition of matter of the formula
• E—Lg
• wherein E is a chromophore;
• L comprises a chemically reactive group that is crosslinkable;
• and g=1-24, where the chromophore has the structure
• 129
• wherein, independently at each occurrence,
• D is an electron donating group having low electron affinity relative to the electron affinity of A;
• π1 is absent or a bridge that provides electronic conjugation between D and the thiophene ring;
• π2 is absent or a bridge that provides electronic conjugation between A and the thiophene ring;
• A is an electron accepting group having high electron affinity relative to the electron affinity of D;
• X is O or S;
• R is alkyl, aryl, heteroalkyl or heteroaryl;
• and
• n is 1, 2, 3 or 4.

An optical router comprising a plurality of switches, wherein each switch comprises:

• 1) an input;
• 2) an output;
• 3) a first waveguide extending between the input and the output;
• and 4) a second waveguide aligned to the first waveguide and positioned for evanescent coupling to the first waveguide;
• wherein at least one of the first and second waveguides comprises a composition of matter of the formula
• E—Lg
• wherein E is a chromophore;
• L comprises a chemically reactive group that is crosslinkable;
• and g=1-24, where the chromophore has the structure
• 130
• wherein, independently at each occurrence,
• D is an electron donating group having low electron affinity relative to the electron affinity of
• 131
• π is absent or a bridge that provides electronic conjugation between D and the double bond adjacent to π;
• and
• R is alkyl, aryl, heteroalkyl or heteroaryl.