Carbene-Functionalized Composite Materials

Patent metadata

Field	Value
Publication number	US-2016199875-A1
Application number	US-201414912900-A
Country	US
Kind code	A1
Filing date	Aug 19, 2014
Priority date	Aug 19, 2013
Publication date	Jul 14, 2016
Grant date	—

Abstract

The present application provides stable, carbene-functionalized composite materials, and methods and uses thereof. These carbene-functionalized composite materials comprise a material having a metal surface, and a carbene monolayer that is uniform, contaminant-free (metal oxide, etc), and more stable than thiol-functionalized monolayers. Uses of such carbene-functionalized composite materials include semi-conducting materials, microelectronic devices, drug delivery or sensing applications.

First claim

We claim:

1 . A carbene-functionalized composite material, comprising:
a carbene monolayer; and a material having at least a metal surface; wherein said carbene monolayer interacts with the metal surface, and is uniform, stable, and/or substantially free of contamination.

2 . The composite material of claim 1 , wherein the carbene monolayer comprises or ≦2% contamination.

3 . The composite material of claims 1 and 2 , wherein the carbene monolayer comprises one or more carbenes of Formula I

wherein:
n is an integer from 1 to 8, or from 1 to 4;
m is an integer from 0 to 4;
A is absent, an aliphatic cycle, a heterocycle, an aromatic ring, a fused aromatic ring system, a heteroaromatic ring, and/or a fused heteroaromatic ring system, each of which is optionally substituted;
X-L-Z is absent, or
X is C or a heteroatom,
L is a divalent moiety, such as C 1 -C 10 alkylene, C 10 -C 20 alkylene, C 1 -C 10 alkenylene, C 10 -C 20 alkenylene, C 1 -C 10 alkynylene, C 10 -C 20 alkynylene, or dextran, a simple sugar, complex sugar, carbohydrate, ether, thioether, amine, polyamine, polyether, and/or polythioether, each of which is optionally substituted;
Z is H, an aliphatic cycle, a heterocycle, an aromatic ring, a fused aromatic ring system, a heteroaromatic ring, a fused heteroaromatic ring system, an organometallic complex, a transition-metal catalyst, a metal-oxide catalyst, a simple sugar, a complex sugar, a carbohydrate, or a chemically derivatizable group, such as —OH, azide, carboxylic acid, carbonyl chloride, anhydride, ester, aldehyde, alcohol, amine, halogen, epoxide, thiirane, aziridine, amino acid, nucleic acid, alkene, alkyne, conjugated diene, thiol, or thioester, each of which is optionally substituted;
each Y or Y′ is independently C or a heteroatom;
each R o is independently H, halogen, the substituent X-L-Z as defined above, C 1 -C 10 alkyl, C 10 -C 20 alkyl, C 1 -C 10 alkenyl, C 10 -C 20 alkenyl, C 1 -C 10 alkynyl, or C 10 -C 20 alkynyl, C 1 -C 10 alkoxyl, C 10 -C 20 alkoxyl, C 3 -C 20 cyclic aliphatic moiety, aryl, heteroaryl, ether, thioether, amine, polyamine, polyether, or polythioether, each of which is optionally substituted; or, two of R o , together with the atoms to which they are attached, are connected to form a cycle, or heterocycle, each of which is optionally substituted; and
R 1 and R 2 are independently absent, at least one lone pair of electrons, H, C 1 -C 10 alkyl, C 10 -C 20 alkylC 1 -C 10 alkenyl, C 10 -C 20 alkenyl, C 1 -C 10 alkynyl, C 10 -C 20 alkynyl, C 3 -C 20 cyclic aliphatic moiety, aryl, heteroaryl, ether, thiol, thioether, amine, polyamine, polyether, polythioether, or polythiol, each of which is optionally substituted; or, one of R 1 or R 2 , with one of R o , together with the atoms to which they are attached, are connected to form a cycle, or heterocycle, each of which is optionally substituted;
wherein, when A is absent or non-aromatic, the dashed line represents an optional double bond; and/or
when A is absent, each Y′ is independently bonded to R o or X-L-Z, as defined above.

4 . The composite material of claims 1 and 2 , wherein the carbene monolayer comprises carbenes of Formula Ia

wherein:
m is an integer from 0 to 4;
each Y is independently C or a heteroatom;
Y 2 and Y 3 are independently C or a heteroatom, and the dashed line represents an optional double bond;
R 1 and R 2 are independently absent, at least one lone pair of electrons, H, C 1 -C 10 alkyl, C 10 -C 20 alkyl, C 1 -C 10 alkenyl, C 10 -C 20 alkenyl, C 1 -C 10 alkynyl, C 10 -C 20 alkynyl, C 3 -C 20 cyclic aliphatic moiety, aryl, heteroaryl, ether, thiol, thioether, amine, polyamine, polyether, polythioether, or polythiol, each of which may be optionally substituted;
R 3 and R 4 are independently H, halogen, the substituent X-L-Z as defined for Formula I, C 1 -C 10 alkyl, C 10 -C 20 alkyl, C 1 -C 10 alkenyl, C 10 -C 20 alkenyl, C 1 -C 10 alkynyl, C 10 -C 20 alkynyl, C 3 -C 20 cyclic aliphatic moiety, C 1 -C 10 alkoxyl, C 10 -C 20 alkoxyl, C 3 -C 20 cyclic aliphatic moiety, aryl, heteroaryl, ether, thiol, thioether, amine, polyamine, polyether, polythioether, or polythiol, each of which is optionally substituted; or, any one of R 3 or R 4 , with any one of R 1 or R 2 , together with the atoms to which they are attached, are connected to form a cycle, or heterocycle, each of which is optionally substituted.

5 . The composite material of any one of claims 1 - 4 , wherein R 1 and R 2 are independently methyl, ethyl, propyl, butyl, isopropyl, phenyl, mesityl, or diisopropylphenyl, each of which is optionally substituted.

6 . The composite material of any one of claims 1 - 5 , wherein the material having at least a metal surface is a metal film on a support.

7 . The composite material of claim 6 , wherein the support is mica, alumina, silica, titania, silicon, glass, indium tin oxide, or any combination thereof.

8 . The composite material of any one of claims 1 - 5 , wherein the material having at least a metal surface is metal nanoparticles.

9 . The composition material of claim 8 , wherein the metal nanoparticles comprise Au, and/or Pd.

10 . The composite material of any one of claims 1 - 5 , wherein the material having at least a metal surface is a metal chip.

11 . The composite material of claim 10 , wherein the metal chip is a surface plasmon resonance (SPR) detector chip.

12 . The composite material of claim 11 , wherein the SPR chip comprises Au.

13 . The composite material of any one of claims 1 - 5 , wherein the material having at least a metal surface is solid metal, such as a metal sheet, a metal film, a metal wire, or a single crystal metal.

14 . The composite material of any one of claims 1 - 13 , wherein the metal surface comprises an alloy, such as steel, brass, bronze, tungsten carbide, calcium carbide, or any combination thereof.

15 . The composite material of any one of claims 1 - 13 , wherein the metal surface comprises Fe, Rh, Ir, Ni, Pd, Pt, Cu, Cr, Ag, or Au, W, or any alloy or other combination thereof.

16 . A method for forming a composite material comprising a carbene monolayer and a material having at least a metal surface, wherein the carbene monolayer interacts with the metal surface and is stable, uniform, and/or substantially free of contamination, said method comprising contacting said metal surface with carbenes, wherein, optionally, said carbenes are of Formula I of claim 3 , and/or Formula Ia of claim 4 .

17 . The method of claim 16 , wherein contacting said metal surface with carbenes comprises immersing the composite material in carbenes.

18 . The method of claim 16 or 17 , wherein the material having at least one metal surface is a metal film on a support, a metal chip, solid metal, a metal wire, a single crystal metal, or metal nanoparticles.

19 . The method of claim 18 , wherein the support is mica, alumina, silica, titania, silicon, glass, indium tin oxide, or a combination thereof.

20 . The method of any one of claims 16 - 19 , wherein the metal surface comprises an alloy such as steel, brass, bronze, tungsten carbide, calcium carbide, or any combination thereof.

21 . The method of any one of claims 16 - 19 , wherein the me

Assignees

• Univ Kingston

Inventors

• Crudden Cathleen M
• Horton Hugh J
• Zenkina Olena V
• Ebralidze Iraklii I
• Smith Christene Anne

Classifications

• G01N21/553

  and using surface plasmons (fluorescence excitation G01N21/648; enhanced Raman G01N21/658) · CPC title

• B32B2457/00

  Electrical equipment · CPC title

• G01N33/54373

  involving physiochemical end-point determination, e.g. wave-guides, FETS, gratings · CPC title

• B05D1/18 Primary

  performed by dipping · CPC title

• G01N21/78

  producing a change of colour · CPC title