Inorganic siloxane ladder composites and methods of their preparation

1. A compound of formula I:

wherein

q is an integer from 1 to 3;

r is an integer from 1 to 10000;

each A 1 , A 2 , A 3 , A 4 , A 5 , A 6 , A 7 , A 8 , A 9 , A 10 , A 11 , and A 12 independently is, —CH 3 , substituted —CH 3 , —CH 2 —C(═O)—H, substituted —CH 2 —C(═O)—H, —C 6 H 5 , substituted —C 6 H 5 , —CH═CH 2 , substituted —CH═CH 2 , —CH 2 —CH═CH 2 , substituted —CH 2 —CH═CH 2 , a metal-aza crown complex, a metal-thio crown complex, or a metal-acrylic acid complex, and wherein at least one of A 1 , A 2 , A 3 , A 4 , A 5 , A 6 , A 7 , A 8 , A 9 , A 10 , A 11 , and A 12 is a metal-aza crown complex or a metal thio crown complex, wherein the metal-aza crown complex of the metal-thio crown complex comprises a metallic nanoparticle selected from a ZrO 2 nanoparticle, a TiO 2 nanoparticle, a ZnS nanoparticle, a ZnO nanoparticle, or any combination thereof complex; and

each A 13 , A 14 , A 15 , and A 16 independently is, —CH 2 — or —CF 2 —.

2. The compound of claim 1 , wherein when any one of A 1 to A 12 is the metal-aza crown complex, the metal-aza crown complex comprises the metallic nanoparticle in contact with an aza crown molecule, and the aza crown molecule is selected from formula IIa or IIb:

wherein

s is an integer from 3 to 12;

each R is independently, —O—, —CF 2 —, —C(═O)—O—, —C(═O)—NH—, or —NH—; and

each R 1 is independently, —H, —F, —CF 3 , —OH, —CF 2 Cl, —NH 2 , a bivalent —O— linked to the siloxane polymer of formula I, a bivalent —CF 2 — linked to the siloxane polymer of formula I, or a bivalent —NH— linked to the siloxane polymer of formula I.

3. The compound of claim 1 , wherein when any one of A 1 to A 12 is the metal-thio crown complex, the metal-thio crown complex comprises a metallic nanoparticle in contact with a thio-crown molecule, and the thio-crown molecule is selected from formula IIIa or IIIb:

wherein:

t is an integer from 3 to 12;

each R is independently, —O—, —CF 2 —, —C(═O)—O—, —C(═O)—NH—, or —NH—; and

each R 1 is independently, —H, —F, —CF 3 , —OH, —CF 2 Cl, —NH 2 , a bivalent —O— linked to the siloxane polymer of formula I, a bivalent —CF 2 — linked to the siloxane polymer of formula I, or a bivalent —NH— linked to the siloxane polymer of formula I.

4. The compound of claim 1 , wherein the metal-aza crown complex is selected from:

wherein:

M is ZrO 2 nanoparticle, TiO 2 nanoparticle, ZnS nanoparticle, or ZnO nanoparticle;

R is —O—, —CF 2 —, —C(═O)—O—, —C(═O)—NH—, or —NH—; and

each R 1 is independently, —H, —F, —CF 3 , —OH, —CF 2 Cl, —NH 2 , a bivalent —O— linked to the siloxane polymer of formula I, a bivalent —CF 2 — linked to the siloxane polymer of formula I, or a bivalent —NH— linked to the siloxane polymer of formula I.

5. The compound of claim 1 , wherein the metal-thio crown complex is selected from:

wherein:

M is ZrO 2 nanoparticle, TiO 2 nanoparticle, ZnS nanoparticle, or ZnO nanoparticle;

R is independently, —O—, —CF 2 —, —C(═O)—O—, —C(═O)—NH—, or —NH—; and

each R 1 is independently, —H, —F, —CF 3 , —OH, —CF 2 Cl, —NH 2 , a bivalent —O— linked to the siloxane polymer of formula I, a bivalent —CF 2 — linked to the siloxane polymer of formula I, or a bivalent —NH— linked to the siloxane polymer of formula I.

6. A compound of formula IV:

wherein:

n is an integer from 1 to 100;

A 17 is a metal-aza crown complex or a metal-thio crown complex;

A 18 is a metal-aza crown complex or a metal-thio crown complex;

A 19 is a metal-aza crown complex or a metal-thio crown complex; and

A 20 is a metal-aza crown complex or a metal-thio crown complex.

7. The compound of claim 6 , wherein when any one of A 17 , A 18 , A 19 , or A 20 is the metal-aza crown complex, the metal-aza crown complex comprises a metallic nanoparticle in contact with an aza crown molecule, and the aza crown molecule is selected from formula IIc or IId:

wherein

s is an integer from 3 to 12;

each R is independently, —O—, —CF 2 —, —C(═O)—O—, —C(═O)—NH—, or —NH—; and

each R 2 is independently, —H, —F, —CF 3 , —OH, —CF 2 Cl, or —NH 2 .

8. The compound of claim 6 , wherein when any one of A 17 , A 18 , A 19 , or A 20 is the metal-thio crown complex, the metal-thio crown complex comprises a metallic nanoparticle in contact with a thio-crown molecule, and the thio-crown molecule is selected from formula IIIc or IIId:

wherein:

t is an integer from 3 to 12;

each R is independently, —O—, —CF 2 —, —C(═O)—O—, —C(═O)—NH—, or —NH—; and

each R 2 is independently, —H, —F, —CF 3 , —OH, —CF 2 Cl, or —NH 2 .

9. The compound of claim 7 , wherein the metallic nanoparticle is a ZrO 2 nanoparticle, a TiO 2 nanoparticle, a ZnS nanoparticle, a ZnO nanoparticle, or any combination thereof.

10. An optical waveguide structure comprising:

a light transmitting core material having a first refractive index; and

a cladding material partially contacting or entirely surrounding the light transmitting core material, wherein the cladding material has a second refractive index lower than the first refractive index of the light transmitting core material, and wherein the light transmitting core material comprises one or more compounds of formula I

wherein:

q is an integer from 1 to 3;

r is an integer from 1 to 10000;

each A 1 , A 2 , A 3 , A 4 , A 5 , A 6 , A 7 , A 8 , A 9 , A 10 , A 11 , and A 12 independently is, —CH 3 , substituted —CH 3 , —CH 2 —C(═O)—H, substituted —CH 2 —C(═O)—H, —C 6 H 5 , substituted —C 6 H 5 , —CH═CH 2 , substituted —CH═CH 2 , —CH 2 —CH═CH 2 , substituted —CH 2 —CH═CH 2 , a metal-aza crown complex, a metal-thio crown complex, or a metal-acrylic acid complex, and wherein at least one of A 1 , A 2 , A 3 , A 4 , A 5 , A 6 , A 7 , A 8 , A 9 , A 10 , A 11 , and A 12 is a metal-aza crown complex or a metal-thio crown complex; and

each A 13 , A 14 , A 15 , and A 16 independently is —CH 2 — or —CF 2 —.

11. A method to make a siloxane compound of formula I, the method comprising:

contacting a metal-crown complex with trifluorochloromethane and a silicon metal to form a dichlorosilane-trifluoromethyl-metal-crown complex;

hydrolyzing the dichlorosilane-trifluoromethyl-metal-crown complex to form a fluorinated siloxane polymer compound of formula IV

wherein:

n is an integer from 1 to 100,

A 17 is a metal-aza crown complex or a metal-thio crown complex,

A 18 is a metal-aza crown complex or a metal-thio crown complex,

A 19 is a metal-aza crown complex or a metal-thio crown complex, and

A 20 is a metal-aza crown complex or a metal-thio crown complex; and

contacting the fluorinated siloxane polymer compound of formula IV with a bis-siloxane D4 compound

and an anionic catalyst to form the siloxane compound of formula I

wherein

q is an integer from 1 to 3;

r is an integer from 1 to 10000;

each A 1 , A 2 , A 3 , A 4 , A 5 , A 6 , A 7 , A 8 , A 9 , A 10 , A 11 , and A 12 independently is, —CH 3 , substituted —CH 3 , —CH 2 —C(═O)—H, substituted —CH 2 —C(═O)—H, —C 6 H 5 , substituted —C 6 H 5 , —CH═CH 2 , substituted —CH═CH 2 , —CH 2 —CH═CH 2 , substituted —CH 2 —CH═CH 2 , a metal-aza crown complex, a metal-thio crown complex, or a metal-acrylic acid complex, and wherein at least one of A 1 , A 2 , A 3 , A 4 , A 5 , A 6 , A 7 , A 8 , A 9 , A 10 , A 11 , and A 12 is a metal-aza crown complex or a metal-thio crown complex; and

each A 13 , A 14 , A 15 , and A 16 independently is —CH 2 — or —CF 2 —.

12. The method of claim 11 , wherein the dichlorosilane-trifluoromethyl-metal-crown complex is formed by contacting a crown macromolecule with a metallic nanoparticle, the crown macromolecule represented by the formula V or VI:

wherein:

each X is —NH— or —S—;

u is an integer from 4 to 12;

v is an integer from 4 to 12; and

each R 3 is independently, —F, —CF 3 , —OH, —CF 2 Cl, —CH 2 Cl, —COCl, or —NH 2 .

13. The method of claim 12 , wherein the metallic nanoparticle is a ZrO 2 nanoparticle, a TiO 2 nanoparticle, a ZnS nanoparticle, a ZnO nanoparticle, or any combination thereof.

14. The method of claim 11 , wherein hydrolyzing the dichlorosilane-trifluoromethyl-metal-crown complex comprises controlled hydrolysis of the dichlorosilane-trifluoromethyl-metal-crown complex.

15. The method of claim 11 , wherein contacting the fluorinated siloxane polymer compound of formula IV comprises contacting with an anionic catalyst including:

16. The method of claim 11 , wherein contacting the metal-crown complex and the trifluorochloromethane comprises contacting at a molar ratio of about 1:1 to about 1:4.

17. The method of claim 11 , wherein contacting the fluorinated siloxane polymer compound of formula IV and the bis-siloxane D4 compound comprises contacting at a molar ratio of about 1:0.1 to about 1:0.5.

18. The compound of claim 8 , wherein the metallic nanoparticle is a ZrO 2 nanoparticle, a TiO 2 nanoparticle, a ZnS nanoparticle, a ZnO nanoparticle, or any combination thereof.

19. The optical waveguide structure of claim 10 , further comprising a substrate in contact with the light transmitting core material.

20. The optical waveguide structure of claim 19 , wherein the substrate is selected from the group consisting of silicon, silicon oxide, silicon oxide/silicon, gallium arsenide, silicon nitride, silica on silicon, glass, plastic, quartz, ceramic, and crystalline material.

21. The optical waveguide structure of claim 10 , wherein the cladding material is selected from the group consisting of silica xerogels, silicon oxide, metal oxides, air, silicon dioxide, benzocyclobutene, plasma oxides, acrylates, fluorinated acrylates, polyimides.