# US 10,865,290 B2 · Compositions and methods relating to living supramolecular polymerization and polymers

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- Number: US 10,865,290 B2
- Document ID: US10865290B2
- Status: Granted
- Kind: B2
- Application number: 15/460,532
- Filed: 2017-03-16
- Published: 2017-09-21
- Granted: 2020-12-15
- Earliest claimed: 2016-03-16
- Assignees: The University of Hong Kong
- Applicants: The University of Hong Kong
- Inventors: Vivian Wing-Wah Yam; Kaka Zhang; Yu-Lut Leung; Margaret Ching-Lam Yeung; Kwun-Wa Chan
- Web page: https://patentgrep.com/patent/US10865290B2

## CPC

- C08K 5/56: Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
- C08F 283/06: on to polyethers, polyoxymethylenes or polyacetals {(C08F283/004 takes precedence)}
- D01F 6/30: comprising olefins as the major constituent
- D01F 6/36: comprising unsaturated carboxylic acids or unsaturated organic esters as the major constituent
- D01F 6/94: of other polycondensation products
- D01F 8/16: with at least one other macromolecular compound obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds as constituent
- B82Y 30/00: Nanotechnology for materials or surface science, e.g. nanocomposites
- B82Y 40/00: Manufacture or treatment of nanostructures
- D10B 2331/06: polyethers
- C08K: Use of inorganic or non-macromolecular organic substances as compounding ingredients (paints, inks, varnishes, dyes, polishes, adhesives C09)
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- D01F: CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- B82Y: SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- D10B: INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES

## Abstract

A supramolecular polymer with living characteristics is provided based on small molecules or metal complexes of a planar or linear geometry and a polymer. The small molecules are solvophobic and can associate or assemble with each other through non-covalent interactions such as but not limited to metal-metal, π-π, hydrogen-bonding, and/or solvophobic-solvophobic interactions, in the modulation of the polymer. The polymer has affinity to the medium (e.g., solvent) and still interacts with the small molecules via non-covalent interactions such as electrostatic attractions to stabilize the associated/assembled small molecules. Varying the composition and/or length of the polymer can modulate the dimensions of the supramolecular polymer and the nanostructures therefrom. The two- or multi-component supramolecular polymer has active ends to support further supramolecular polymerization upon addition of small molecules of a planar or linear geometry. A process of two-component living supramolecular polymerization is also provided.

## Claims

### Claim 1

A supramolecular polymer having active ends for propagation or elongation, comprising
a plurality of first small-molecule components, wherein the first small-molecule components have a planar or linear geometry, wherein the first small molecule components are solvophobic, and wherein the first small-molecule components are associated with one another non-covalently based on interactions comprising metal-metal interactions, π-π interactions electrostatic attractions, hydrogen-bonding interactions, solvophobic-solvophobic interactions, or a combination thereof; and
a polymer component, wherein the polymer component is solvophilic, and wherein the polymer component is in a non-covalent interaction with some or all of the first small-molecule components,
wherein the supramolecular polymer has a nanostructure, wherein the nanostructure is in a form comprising nanofibers, nanorods, nano-belts, nano-ribbons, or nano-wires, and
wherein the supramolecular polymer has active ends, wherein the active ends are capable of being propagated or elongated by addition of a plurality of second small-molecule components, wherein the second small-molecule components have a planar or linear geometry, wherein the second small molecule components are solvophobic, wherein the second small-molecule components are associated with one another non-covalently based on interactions comprising metal-metal interactions, π-π interactions, electrostatic attractions, hydrogen-bonding interactions, solvophobic-solvophobic interactions, or a combination thereof, and wherein the second small-molecule components can be the same as or different from the first small-molecule components.

### Claim 2 (depends on 1)

The supramolecular polymer of claim 1, wherein the supramolecular polymer has a core-shell structure, wherein the shell comprises at least a portion of the polymer component and the core comprises the first small-molecule components.

### Claim 3 (depends on 1)

The supramolecular polymer of claim 1, wherein the first small-molecule components comprise metal complexes of a square-planar configuration, wherein the metal complex is defined by the following formula,
wherein:
(a) M is Ni(II), Pd(II), Pt(II), Rh(I), Ir(I), Au(III), Zn(II), or Cu(II);
(b) L1, L2, L3, and L4 represent ligands with donor atoms independently selected from N, C, O, S, Se, P, and As;
(c) dashed lines represent optional covalent linkages between neighboring ligands; and
(d) n+/− represents the number of positive charges or negative charges carried by the metal complexes, and n is selected from 0, 1, 2, 3, 4, 5, and 6.

### Claim 4 (depends on 1)

The supramolecular polymer of claim 1, wherein the first small-molecule components comprise metal complexes of a trigonal-planar configuration, wherein the metal complex is defined by the following formula,
wherein:
(a) M is Cu(I), Ag(I), Au(I), Ni(0), Pd(0), Pt(0), Zn(II), Cd(II), or Hg(II);
(b) L1, L2, and L3 represent ligands with donor atoms independently selected from N, C, O, S, Se, P, and As;
(c) dashed lines represent optional covalent linkages between neighboring ligands; and
(d) n+/− represents the number of positive charges or negative charges carried by the metal complexes, and n is selected from 0, 1, 2, 3, 4, 5, and 6.

### Claim 5 (depends on 1)

The supramolecular polymer of claim 1, wherein the first small-molecule components comprise metal complexes of a linear configuration, wherein the metal complex is defined by the following formula,
wherein:
(a) M is Cu(I), Ag(I), Au(I), Ni(0), Pd(0), Pt(0), Zn(II), Cd(II) or Hg(II);
(b) L1 and L2 represent ligands with donor atoms independently selected from N, C, O, S, Se, P, and As; and
(c) n+/− represents the number of positive charges or negative charges carried by the metal complexes, and n is selected from 0, 1, 2, 3, 4, 5, and 6.

### Claim 6 (depends on 1)

The supramolecular polymer of claim 1, wherein the first small-molecule components comprise planar organic molecules that are positively charged, negatively charged, or charge-neutral.

### Claim 7 (depends on 1)

The supramolecular polymer of claim 1, wherein the first small-molecule components comprise an alkynylplatinum(II) terpyridine complex defined by the following formula,
wherein
R1 is H, or substituted, unsubstituted, or heteroatom-containing C1-C30 alkyl, C2-C30 alkenyl, C3-C30 aryl, C3-C30 heteroaryl, C1-C30 alkoxy, C3-C30 aryloxy, C3-C30 arylthio, C1-C30 alkylthio, C2-C30 carbonyl, C1-C30 carboxyl, amino, amido, or polyaryl;
m is an integer between 1 and 20;
R2, R3, R4, R5, R6, R7, R8, R9, R10, R11 and R12 are, independently, H, C1-C30 alkyl, C2-C30 alkenyl, C2-C30 alkynyl, C3-C30 aryl, or N-substituted amide;
n+/− represents the number of positive charges or negative charges carried by the metal complexes, and n is selected from 0, 1, 2, 3, 4, 5 and 6; and
Xn− is an anion comprising a chloride (Cr), nitrate (NO3−), triflate (OTf−), hexafluorophosphate (PF6−), perchlorate (ClO4−), tetrafluoroborate (BF4−), or tetraphenylboronate (BPh4−); and Xn+ is a cation comprising a Na+, K+, Ca2+, Mg2+, bis(triphenylphosphine)iminium (PPN+), quaternary ammonium cation, pyridinium cation or a phosphonium cation.

### Claim 8 (depends on 1)

The supramolecular polymer of claim 1, wherein the first small-molecule components comprise a platinum(II) 2,6-bis(benzimidazol-2′-yl)pyridine complex defined by the following formula,
wherein
R13 comprises C1 or C≡C—R′, where R′ is H or substituted or unsubstituted C1-C30 alkyl, C2-C30 alkenyl, C3-C30 aryl, C3-C30 heteroaryl, C1-C30 alkoxy, C3-C30 aryloxy, C3-C30 arylthio, C1-C30 alkylthio, C2-C30 carbonyl, C1-C30 carboxyl, amino, amido, or polyaryl;
R14 and R15 are independently H or substituted or unsubstituted C1-C30 alkyl, C2-C30 alkenyl, C2-C30 alkynyl, C3-C30 aryl, C3-C30 heteroaryl, C1-C30 alkoxy, C3-C30 aryloxy, C3-C30 arylthio, C1-C30 alkylthio, C2-C30 carbonyl, C1-C30 carboxyl, amino, amido, or polyaryl; and
X− is an anion comprising chloride, nitrate, triflate, hexafluorophosphate, perchlorate, tetrafluoroborate, or tetraphenylboronate.

### Claim 9 (depends on 1)

The supramolecular polymer of claim 1, wherein the first small-molecule components are selected from the group consisting of
wherein X− is an anion comprising chloride, nitrate, triflate, hexafluorophosphate, perchlorate, tetrafluoroborate, or tetraphenylboronate.

### Claim 10 (depends on 1)

The supramolecular polymer of claim 1, wherein the polymer component comprises a block copolymer, wherein at least one block is a polymer selected from a group consisting of poly(acrylic acid), poly(acrylate), poly(methacrylic acid), poly(methacrylate), poly(acrylamide), poly(methacrylamide), poly(alkylene oxide), polyphosphite, polyphosphonate, polyphosphate, polyphosphoramidate, poly(carbonate), poly(ester), poly(anhydride), poly(urethane), poly(diene), poly(acetylene), poly(alkene), poly(vinyl ether), poly(vinyl alcohol), poly(vinyl ketone), poly(vinyl halide), poly(vinyl nitrite), poly(vinyl ester), poly(styrene), poly(vinyl pyridine), quaternized poly(vinyl pyridine), polyethylenimine, poly(lysine), polyphosphonium, polysulfonium, poly(amide), poly(amino acid), poly(lactic acid), poly(saccharide), DNA, RNA, poly(aromatic sulfonate), quaternized poly(arylamine), polyvinylpyrrolidone, poly(ethylene glycol), poly(alkylaminoacrylate), and derivatives thereof, and copolymers thereof.

### Claim 11 (depends on 10)

The supramolecular polymer of claim 10, wherein the polymer component is a poly(ethylene glycol)-b-poly(acrylic acid).

### Claim 12 (depends on 1)

The supramolecular polymer of claim 1, wherein the polymer component comprises an amphiphilic polymeric surfactant comprising poly(acrylic acid), poly(acrylate), poly(methacrylic acid), poly(methacrylate), poly(acrylamide), poly(methacrylamide), poly(oxide), polyphosphite, polyphosphonate, polyphosphate, polyphosphoramidate, poly(carbonate), poly(ester), poly(anhydride), poly(urethane), poly(diene), poly(acetylene), poly(alkene), poly(vinyl ether), poly(vinyl alcohol), poly(vinyl ketone), poly(vinyl halide), poly(vinyl nitrite), poly(vinyl ester), poly(styrene), poly(vinyl pyridine), quaternized poly(vinyl pyridine), polyethylenimine, poly(lysine), polyphosphonium, polysulfonium, poly(amide), poly(amino acid), poly(lactic acid), poly(saccharide), DNA, RNA, poly(aromatic sulfonate), quaternized poly(arylamine), polyvinylpyrrolidone, poly(ethylene glycol), poly(alkylaminoacrylate), copolymers thereof, solvophobically modified derivatives thereof, or hydrophobically modified derivatives thereof.

### Claim 13 (depends on 1)

The supramolecular polymer of claim 1, wherein the first small-molecule components and the polymer component have a range of molar ratio between about 0.005:1 and about 50:1.

### Claim 14

A method comprising incubating, in a solvent, first small-molecule components and a polymer component for a period of time effective to induce formation of supramolecular polymers,
wherein the first small-molecule components have a planar or linear geometry, wherein the first small molecule components are solvophobic, and wherein the first small-molecule components associate with one another non-covalently based on interactions comprising metal-metal interactions, π-π interactions, electrostatic attractions, hydrogen-bonding interactions, solvophobic-solvophobic interactions, or a combination thereof,
wherein the polymer component is solvophilic, and wherein the polymer component interacts with some or all of the first small-molecule components non-covalently to stabilize the formed supramolecular polymers, and
wherein the formed supramolecular polymers have active ends capable of propagation or elongation upon addition of additional small-molecule components.

### Claim 15 (depends on 14)

The method of claim 14, wherein the formed supramolecular polymers have one or more nanostructures, wherein the nanostructure is in a form comprising nanofibers, nanorods, nano-belts, nano-ribbons, or nano-wires.

### Claim 16 (depends on 14)

The method of claim 14, wherein the formed supramolecular polymers have a core-shell structure, wherein the shell comprises at least a portion of the polymer component and the core comprises the first small-molecule components.

### Claim 17 (depends on 14)

The method of claim 14, wherein the first small-molecule components comprise metal complexes of a square-planar configuration, defined by the following formula,
wherein:
(a) M is Ni(II), Pd(II), Pt(II), Rh(I), Ir(I), Au(III), Zn(II), or Cu(II);
(b) L1, L2, L3, and L4 represent ligands with donor atoms independently selected from N, C, O, S, Se, P, and As;
(c) dashed lines represent optional covalent linkages between neighboring ligands; and
(d) n+/− represents the number of positive charges or negative charges carried by the metal complexes, and n is selected from 0, 1, 2, 3, 4, 5, and 6.

### Claim 18 (depends on 14)

The method of claim 14, wherein the first small-molecule components comprise metal complexes of a trigonal-planar configuration, defined by the following formula,
wherein:
(a) M is Cu(I), Ag(I), Au(I), Ni(0), Pd(0), Pt(0), Zn(II), Cd(II), or Hg(II);
(b) L1, L2, and L3 represent ligands with donor atoms independently selected from N, C, O, S, Se, P, and As;
(c) dashed lines represent optional covalent linkages between neighboring ligands; and
(d) n+/− represents the number of positive charges or negative charges carried by the metal complexes, and n is selected from 0, 1, 2, 3, 4, 5, and 6.

### Claim 19 (depends on 14)

The method of claim 14, wherein the first small-molecule components comprise metal complexes of a linear configuration, defined by the following formula,
wherein:
(a) M is Cu(I), Ag(I), Au(I), Ni(0), Pd(0), Pt(0), Zn(II), Cd(II) or Hg(II);
(b) L1 and L2 represent ligands with donor atoms independently selected from N, C, O, S, Se, P, and As; and
(c) n+/− represents the number of positive charges or negative charges carried by the metal complexes, and n is selected from 0, 1, 2, 3, 4, 5, and 6.

### Claim 20 (depends on 14)

The method of claim 14, wherein the first small-molecule components comprise planar organic molecules that are positively charged, negatively charged, or charge-neutral.

### Claim 21 (depends on 14)

The method claim 14, wherein the polymer component comprises—a block copolymer, wherein at least one block is solvophilic and at least one block can bind to the first small-molecule components through non-covalent interactions selected from the group consisting of electrostatic attractions, hydrogen-bonding interactions, solvophobic-solvophobic interactions, and π-π interactions.

### Claim 22 (depends on 21)

The method of claim 21, wherein the block copolymer comprises at least one block selected from the group consisting of poly(acrylic acid), poly(acrylate), poly(methacrylic acid), poly(methacrylate), poly(acrylamide), poly(methacrylamide), poly(alkylene oxide), polyphosphite, polyphosphonate, polyphosphate, polyphosphoramidate, poly(carbonate), poly(ester), poly(anhydride), poly(urethane), poly(diene), poly(acetylene), poly(alkene), poly(vinyl ether), poly(vinyl alcohol), poly(vinyl ketone), poly(vinyl halide), poly(vinyl nitrite), poly(vinyl ester), poly(styrene), poly(vinyl pyridine), quaternized poly(vinyl pyridine), polyethylenimine, poly(lysine), polyphosphonium, polysulfonium, poly(amide), poly(amino acid), poly(lactic acid), poly(saccharide), DNA, RNA, poly(aromatic sulfonate), quaternized poly(arylamine), polyvinylpyrrolidone, poly(ethylene glycol), poly(alkylaminoacrylate), and derivatives thereof, and copolymers thereof.

### Claim 23 (depends on 14)

The method of claim 14, wherein the polymer component comprises an amphiphilic polymeric surfactant comprising poly(acrylic acid), poly(acrylate), poly(methacrylic acid), poly(methacrylate), poly(acrylamide), poly(methacrylamide), poly(oxide), polyphosphite, polyphosphonate, polyphosphate, polyphosphoramidate, poly(carbonate), poly(ester), poly(anhydride), poly(urethane), poly(diene), poly(acetylene), poly(alkene), poly(vinyl ether), poly(vinyl alcohol), poly(vinyl ketone), poly(vinyl halide), poly(vinyl nitrite), poly(vinyl ester), poly(styrene), poly(vinyl pyridine), quaternized poly(vinyl pyridine), polyethylenimine, poly(lysine), polyphosphonium, polysulfonium, poly(amide), poly(amino acid), poly(lactic acid), poly(saccharide), DNA, RNA, poly(aromatic sulfonate), quaternized poly(arylamine), polyvinylpyrrolidone, poly(ethylene glycol), poly(alkylaminoacrylate), copolymers thereof, solvophobically modified derivatives thereof, or hydrophobically modified derivatives thereof.

### Claim 24 (depends on 14)

The method of claim 14, wherein the first small-molecule components and the polymer component in the solvent have a range of molar ratio between about 0.005:1 and about 50:1.

### Claim 25 (depends on 14)

The method of claim 14, further comprising propagating or elongating the formed supramolecular polymers by incubating the additional small-molecule components with the formed supramolecular polymers,
wherein the additional small-molecule components have a planar or linear geometry and associate non-covalently with one another, with the first small-molecule components, or both, and
wherein the polymer component of the formed supramolecular polymers interacts with the additional small-molecule components.

### Claim 26 (depends on 25)

The method of claim 25, wherein the additional small-molecule components are identical to the first small-molecule components.

### Claim 27 (depends on 25)

The method of claim 25, wherein the additional small-molecule components are different from the first small-molecule components.

### Claim 28 (depends on 14)

The method of claim 14, wherein the solvent comprises water.

### Claim 29 (depends on 14)

The method of claim 14 further comprising fabricating aligned metal nanoparticles or nanowires using the formed supramolecular polymer as precursors.

### Claim 30 (depends on 14)

The method of claim 14, wherein the polymer component is in excess after the supramolecular polymers are formed.

### Claim 31

A multi-component supramolecular polymer comprising a plurality of supramolecular polymers, wherein the supramolecular polymers independently comprise
a plurality of small-molecule components, wherein the small-molecule components have a planar or linear geometry, wherein the small molecule components are solvophobic, and wherein the small-molecule components are associated with one another non-covalently based on interactions comprising metal-metal interactions, π-π interactions, electrostatic attractions, hydrogen-bonding interactions, solvophobic-solvophobic interactions, or a combination thereof; and
a polymer component, wherein the polymer component is solvophilic, and wherein the polymer component is in a non-covalent interaction with some or all of the small-molecule components,
wherein the polymer component is the same among the supramolecular polymers and the small molecule components are the same or different among the supramolecular polymers,
wherein the supramolecular polymers independently have a nanostructure with a plurality of ends, wherein the nanostructure is in a form comprising nanofibers, nanorods, nano-belts, nano-ribbons, or nano-wires,
wherein the supramolecular polymers are associated with one another through a junction connecting (i) one of the ends from one supramolecular polymer in the plurality of supramolecular polymers and (ii) one of the ends from another supramolecular polymer in the plurality of supramolecular polymers.