# US 2019/0169132 A1 · Methods of Forming Carbene-Functionalized Composite Materials

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- Number: US 2019/0169132 A1
- Document ID: US20190169132A1
- Status: Published application
- Kind: A1
- Application number: 15/773,811
- Filed: 2016-11-02
- Published: 2019-06-06
- Earliest claimed: 2015-11-06
- Assignees: Queen's University at Kingston
- Applicants: Queen's University at Kingston
- Inventors: Cathleen M. Crudden; J. Hugh Horton; Mina Raafat Ryad Narouz; Phillip Unsworth; Zhijun Li; Ali Nazemi; Joseph Daniel Padmos; Patrick Eisenberger; Matthew Thomas Zamora; Michael William Angus MacLean
- Web page: https://patentgrep.com/patent/US20190169132A1

## CPC

- C07D 235/08: Radicals containing only hydrogen and carbon atoms
- C07D 233/56: with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
- C07D 403/12: linked by a chain containing hetero atoms as chain links
- C07D 471/04: Ortho-condensed systems
- C07D 487/04: Ortho-condensed systems
- C23C 22/02: using non-aqueous solutions
- G01N 21/554: {detecting the surface plasmon resonance of nanostructured metals, e.g. localised surface plasmon resonance}
- G01N 33/54353: {with ligand attached to the carrier via a chemical coupling agent (coatings G01N33/54393)}
- B82Y 30/00: Nanotechnology for materials or surface science, e.g. nanocomposites
- C07D: HETEROCYCLIC COMPOUNDS (macromolecular compounds C08)
- C23C: COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL (making metal-coated products by extrusion B21C23/22; covering with metal by connecting pre-existing layers to articles, see the relevant places, e.g. B21D39/00, B23K; metallising of glass C03C; metallising mortars, concrete, artificial stone, ceramics or natural stone C04B41/00; enamelling of, or applying a vitreous layer to, metals C23D; treating metal surfaces or coating of metals by electrolysis or electrophoresis C25D; single-crystal film growth C30B; by metallising textiles D06M11/83; decorating textiles by locally metallising D06Q1/04)
- G01N: INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES (measuring or testing apparatus or processes other than immunoassay, involving enzymes or microorganisms C12M, C12Q)
- B82Y: SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES

## Abstract

Deposition of carbene monolayers that excluded starting anions, such as iodide ions, has been achieved. Anions such as iodide are a typical contaminant in carbene hydrogen carbonate salts when synthesized using the state-of-the-art method. A method is described for eliminating substantially all starting anion (e.g., iodide) contamination from the monolayer. Air stable, purified carbenes precursors were used to deposit an intact monolayer on the surface of some industrially relevant metals. The monolayer's ability to protect these metals against, for example, oxidation has been demonstrated.

## Claims

### Claim 1

A method for forming a carbene-functionalized composite material, comprising:
forming a carbene precursor by
oxidizing a starting anion of a carbene precursor in the presence of water and CO2, or exchanging a starting anion of a carbene salt via a hydrogen carbonate-anion exchange resin, and
forming a purified carbene precursor comprising a final hydrogen carbonate anion that is substantially free of the starting anion;
placing a material having at least a metal surface in fluid communication with the purified carbene precursor, thermally decomposing the purified precursor in the presence of a material having at least a metal surface, or vacuum depositing the purified carbene precursor in the presence of a material having at least a metal surface; and
forming a carbene monolayer on the metal surface, the monolayer being uniform, stable, substantially free of contamination, and substantially free of the starting anion.

### Claim 2 (depends on 1)

The method of claim 1, wherein the purified carbene precursor comprises ≤10% of the starting anion; or, ≤5%; or, ≤2%; or, ≤1%; or, ≤1.5%; or, ≤0.1%.

### Claim at position 3

-5. (canceled)

### Claim 6 (depends on 1)

The method of claim 1, wherein the purified carbene precursor is a compound of
Formula II
wherein:
n is an integer from 1 to 8, or from 1 to 4;
m is an integer from 0 to 4;
each Y or Y′ is independently C or a heteroatom;
B is hydrogen carbonate;
A is absent, an aliphatic cycle, a heterocycle, an aromatic ring, a fused aromatic ring system, a heteroarotnatic 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 C1-C10 alkylene, C10-C20 alkylene, C1-C10 alkenylene, C10-C20 alkenylene, C1-C10 alkynylene, C10-C20 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 N-heterocyclic carbene precursor, 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 hydroxyl (—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 Ro is independently H, halogen, the substituent X-L-Z as defined above, C1-C10 alkyl, C10-C20 alkyl, C1-C10 alkenyl, C10-C20 alkenyl, C1-C10 alkynyl, C10-C20 alkynyl, C1-C10 alkoxyl, C10-C20 alkoxyl, C3-C20 cyclic aliphatic moiety, aryl, heteroaryl, ether, thioether, amine, polyamine, polyether, or polythioether, each of which is optionally substituted; or, two of Ro, together with the atoms to which they are attached, are connected to form a cycle, heterocycle, or an N-heterocyclic carbene precursor, each of which is optionally substituted; and
R1 and R2 are independently absent, at least one lone pair of electrons, H, the substituent X-L-Z as defined above, C1-C10 alkyl, C10-C20 alkyl, C1-C10 alkenyl, C10-C20 alkenyl, C1-C10 alkynyl, C10-C20 alkynyl, C3-C20 cyclic aliphatic moiety, aryl, benzyl, polycyclic aryl, polycyclic benzyl, heteroaryl, ether, thiol, thioether, amine, polyamine, polyether, polythioether, or polythiol, each of which is optionally substituted; or, one of R1 or R2, with one of Ro, 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
when A is absent, each Y′ is independently bonded to Ro or X-L-Z, as defined above;
wherein:
m is an integer from 0 to 4;
each Y is independently C or a heteroatom;
Y2 and Y3 are independently C or a heteroatom, and the dashed line is an optional double bond;
B is hydrogen carbonate;
R3 and R4 are independently absent, at least one lone pair of electrons, H, the substituent X-L-Z as defined for Formula II, C1-C10 alkyl, C10-C20 alkyl, C1-C10 alkenyl, C10-C20 alkenyl, C1-C10 alkynyl, C10-C20 alkynyl), cycloalkyl, aryl, benzyl, polycyclic aryl, polycyclic benzyl, heteroaryl, ether, thiol, thioether, amine, polyamine, polyether, polythioether, or polythiol, each of which is optionally substituted; and
R5 and R6 are independently H, halogen, the substituent X-L-Z as defined for Formula II, C1-C10 alkyl, C10-C20 alkyl, C1-C10 alkenyl, C10-C20 alkenyl, C1-C10 alkynyl, C10-C20 alkynyl, C1-C10 alkoxyl, C10-C20 alkoxyl, C3-C20 cyclic aliphatic, aryl, heteroaryl, ether, thiol, thioether, amine, polyamine, polyether, polythioether, or polythiol, each of which is optionally substituted; or, any one of R5 or R6, with any one of R3 or R4, together with the atoms to which they are attached, are connected to form a cycle, or heterocycle, each of which is optionally substituted; or, any one of R5 or R6, together with the atoms to which they are attached, are connected to form a cycle, heterocycle, or an N-heterocyclic carbene precursor, each of which is optionally substituted;
wherein:
n is an integer from 1 to 8, or from 1 to 4;
m is an integer from 0 to 4;
each Y or Y′ is independently C or a heteroatom;
B is hydrogen carbonate;
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 C10-C20 alkylene, C10-C20 alkenylene, C10-C20 alkynylene, dextran, a simple sugar, complex sugar, carbohydrate, ether, thioether, polyether, and/or polythioether, each of which is optionally substituted;
Z′ is H, or L′, as defined above;
each Rq is independently H, halogen, the substituent X-L′-Z′ as defined above, C10-C20 alkyl, C10-C20 alkenyl, C10-C20 alkynyl, C10-C20 alkoxyl, C6-C20 cyclic aliphatic moiety, aryl, ether, thioether, polyether, or polythioether, each of which is optionally substituted; or, two of Rq, together with the atoms to which they are attached, are connected to form a cycle, which is optionally substituted; and
R7 and R8 are independently absent, at least one lone pair of electrons, H, the substituent X-L′-Z′ as defined above, C1-C10 alkyl, C10-C20 alkyl, C1-C10 alkenyl, C10-C20 alkenyl, C1-C10 alkynyl, C10-C20 alkynyl, C6-C20 cyclic aliphatic moiety, aryl, benzyl, polycyclic aryl, polycyclic benzyl, ether, thiol, thioether, polyether, polythioether, or polythiol, each of which is optionally substituted; or, one of R7 or R8, with one of Rq, together with the atoms to which they are attached, are connected to form a cycle, which is optionally substituted;
wherein, when A is absent or non-aromatic, the dashed line represents an optional double bond; and
when A is absent, each Y′ is independently bonded to Rq or X-L′-Z′, as defined above; or
wherein:
m is an integer from 0 to 4;
each Y is independently C or a heteroatom;
Y2 and Y3 are independently C or a heteroatom, and the dashed line is an optional double bond;
B is hydrogen carbonate;
R9 and R10 are independently absent, at least one lone pair of electrons, H, the substituent X-L′-Z′ as defined above, C1-C10 alkyl, C10-C20 alkyl, C1-C10 alkenyl, C10-C20 alkenyl, C1-C10 alkynyl, C10-C20 alkynyl, C6-C20 cyclic aliphatic moiety, aryl, benzyl, polycyclic aryl, polycyclic benzyl, ether, thiol, thioether, polyether, polythioether, or polythiol, each of which may be optionally substituted;
R11 and R12 are independently H, the substituent X-L′-Z′ as defined for Formula V, C10-C20 alkyl, C10-C20 alkenyl, C10-C20 alkynyl, C6-C20 cyclic aliphatic moiety, C10-C20 alkoxyl, aryl, ether, thioether, polyether, or polythioether, each of which is optionally substituted; or, any one of R11 or R12, with any one of R9 or R10, together with the atoms to which they are attached, are connected to form a cycle, which is optionally substituted.

### Claim 7 (depends on 6)

The method of claim 6, wherein for
Formula (II) or Formula (V): n is 3 or 4; m is 1; each Y is N; each Y′ is C; A is an aromatic ring; X-L-Z or X-L′-Z′ is absent when n is 4; X-L-Z or X-L′-Z′ is present when n is 3; Ro or Rq is H; and, R1 and R2 or R7 and R8 are independently methyl, ethyl, propyl, isopropyl, butyl, isobutyl, hexyl, phenyl, benzyl, mesityl, or 1,3-diisopropylphenyl; or
Formula (IIa) or Formula (Va): m is 1; each Y is N; Y2 and Y3 are C; R5 and R6 or R11 and R12 are independently H or, X-L-Z or X-L′-Z′; and, R3 and R4 or R9 and R10 are independently methyl, ethyl, propyl, isopropyl, butyl, isobutyl, hexyl, phenyl, benzyl, mesityl, or 1,3-diisopropylphenyl.

### Claim 8 (depends on 1)

The method of claim 1, wherein the material having at least a metal surface comprises a (i) metal film on a support; (ii) metal nanoparticles; (iii) metal nanoclusters; (iv) metal nanoworms; (v) a metal chip; (vi) metal coating; or solid metal.

### Claim 9

(canceled)

### Claim 10 (depends on 8)

The method of claim 8, wherein when the material comprises a metal chip, the metal chip is a surface plasmon resonance (SPR) detector chip.

### Claim 11 (depends on 1)

The method of claim 1, wherein the metal surface comprises Mg, Al, Ti, Ga, Fe, Rh, Ir, Ni, Pd, Pt, Ru, Co, Cr, Cu, Ag, Au, W, Ta, Nb, Re, Mo, or any combination or alloy thereof.

### Claim 12

(canceled)

### Claim 13 (depends on 7)

The method of claim 7, wherein the metal surface is functionalized with a chemical species that can be displaced by a carbene.

### Claim 14

(canceled)

### Claim 15

A method for forming a carbene-functionalized composite material, comprising:
forming a carbene precursor by
oxidizing a starting anion of a carbene precursor in the presence of water and CO2, or exchanging a starting anion of a carbene precursor via a hydrogen carbonate-anion exchange resin, and
forming a purified carbene precursor comprising a final hydrogen carbonate anion that is substantially free of the starting anion;
reducing a metal salt in the presence of the purified carbene precursor; and
forming a carbene-functionalized composite material,
the composite material comprising carbene-functionalized nanoparticles or nanoclusters.

### Claim 16

(canceled)

### Claim 17 (depends on 15)

The method of claim 15, wherein reducing a metal salt comprises (i) reducing the metal salt in the presence of a reducing agent; (ii) reducing the metal salt at an elevated temperature; (iii) electrochemically reducing the metal salt; or (iv) photochemically reducing the metal salt.

### Claim at position 16

-19. (canceled)

### Claim 20 (depends on 17)

The method of claim 17, wherein the reducing agent is NaBH4.

### Claim at position 18

-24. (canceled)

### Claim 25 (depends on 15)

The method of claim 15, wherein the metal salt comprises Mg, Al, Ti, Fe, Rh, Ir, Ni, Pd, Pt, Ru, Co, Cr, Cu, Ag, Au, W, Ta, Nb, Re, Mo, or any combination thereof.

### Claim 26 (depends on 6, 15)

The method of claim 15, wherein the purified carhene precursor is a compound of
as defined in claim 6.

### Claim 27

(canceled)

### Claim 28

A carbene-functionalized composite material, comprising:
a material having at least a metal surface; and
a carbene monolayer that is uniform, stable, and substantially free of contamination,
the monolayer being sourced from a purified carbene precursor;
wherein:
the monolayer interacts with the metal surface; and
the purified precursor is sourced from a carbene precursor having a starting anion that is exchanged for a final hydrogen carbonate anion such that the purified precursor and the monolayer is substantially free of the starting anion.

### Claim 29

(canceled)

### Claim 30 (depends on 28)

The composite material of claim 28, wherein the monolayer comprises ≤5% contamination; or, ≤2%.

### Claim 31

(canceled)

### Claim 32 (depends on 6, 28)

The composite material of claim 28, wherein the purified carbene precursor is a compound of
as defined in claim 6.

### Claim at position 27

-35. (canceled)

### Claim 36 (depends on 28)

The composite material of claim 28, wherein the material having at least a metal surface is a surface plasmon resonance (SPR) detector chip.

### Claim 37 (depends on 28)

The composite material of claim 28, wherein the metal surface comprises Mg, Al, Ti, Ga, Fe, Rh, Ir, Ni, Pd, Pt, Ru, Co, Cr, Cu, Ag, Au, W, Ta, Nb, Re, Mo, or any combination or alloy thereof.

### Claim at position 30

-39. (canceled)

### Claim 40 (depends on 28)

The composite material of claim 28, wherein the composite material comprises carbene-functionalized nanoclusters or carbene-functionalized nanoparticles.

### Claim 41 (depends on 40)

The composite material of claim 40, wherein the nanoclusters consist essentially of [Au11(PPh3)7(NHC-iPr)Cl2]Cl, [Au11(PPh3)6-7(NHC-Et)1-2Cl2]Cl, or 1,3-diisopropylbenzimidazolylidene-functionalized Cu nanoclusters.

### Claim at position 33

-44. (canceled)

### Claim 45

A carbene-functionalized composite material comprising:
a lipid layer or a polysaccharide matrix;
a material having at least one metal surface;
a carbene monolayer that is uniform, stable, and substantially free of contamination,
the monolayer being sourced from a purified carbene precursor;
wherein:
the monolayer interacts with the metal surface and the lipid layer or polysaccharide matrix, the monolayer being located between the lipid layer or polysaccharide matrix and the metal surface; and
the purified precursor is sourced from a carbene precursor having a starting anion that is exchanged for a final hydrogen carbonate anion such that the purified precursor and the monolayer is substantially free of the starting anion.

### Claim at position 35

-57. (canceled)

### Claim 58 (depends on 1)

The method of claim 1, wherein the carbene-functionalized composite material is for:
making nano-patterns on semi-conducting surfaces;
fabricating electronic or microelectronic devices;
altering properties of a metal surface (e.g., altering electronic properties of a metal surface);
adherence to a substrate (e.g., an optionally coated second metal u ace);
protecting a metal surface from corrosion or oxidation;
biomedical applications (e.g., drug delivery);
electrochemically detecting molecules;
electrochemical biosensing;
surface plasmon resonance for detecting molecules;
making electrochemical sensors;
sensing applications;
detecting molecules (e.g., biomolecules);
antibacterial/antimicrobial applications;
generating a catalyst;
catalysis; or
colourimetric analysis of molecules (e.g., biomolecules).

### Claim at position 37

-75. (canceled)