Compositions and methods relating to living supramolecular polymerization and polymers

Patent metadata

Field	Value
Publication number	US-10865290-B2
Application number	US-201715460532-A
Country	US
Kind code	B2
Filing date	Mar 16, 2017
Priority date	Mar 16, 2016
Publication date	Dec 15, 2020
Grant date	Dec 15, 2020

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.

First claim

We 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.

2. 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.

3. 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) L 1 , L 2 , L 3 , and L 4 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.

4. 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) L 1 , L 2 , and L 3 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.

5. 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) L 1 and L 2 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.

6. 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.

7. The supramolecular polymer of claim 1 , wherein the first small-molecule components comprise an alkynylplatinum(II) terpyridine complex defined by the following formula,

wherein
R 1 is H, or substituted, unsubstituted, or heteroatom-containing C 1 -C 30 alkyl, C 2 -C 30 alkenyl, C 3 -C 30 aryl, C 3 -C 30 heteroaryl, C 1 -C 30 alkoxy, C 3 -C 30 aryloxy, C 3 -C 30 arylthio, C 1 -C 30 alkylthio, C 2 -C 30 carbonyl, C 1 -C 30 carboxyl, amino, amido, or polyaryl;
m is an integer between 1 and 20;
R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 and R12 are, independently, H, C 1 -C 30 alkyl, C 2 -C 30 alkenyl, C 2 -C 30 alkynyl, C 3 -C 30 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
X n− is an anion comprising a chloride (Cr), nitrate (NO 3 − ), triflate (OTf − ), hexafluorophosphate (PF 6 − ), perchlorate (ClO 4 − ), tetrafluoroborate (BF 4 − ), or tetraphenylboronate (BPh 4 − ); and X n+ is a cation comprising a Na + , K + , Ca 2+ , Mg 2+ , bis(triphenylphosphine)iminium (PPN + ), quaternary ammonium cation, pyridinium cation or a phosphonium cation.

8. 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
R 13 comprises C 1 or C≡C—R′, where R′ is H or substituted or unsubstituted C 1 -C 30 alkyl, C 2 -C 30 alkenyl, C 3 -C 30 aryl, C 3 -C 30 heteroaryl, C 1 -C 30 alkoxy, C 3 -C 30 aryloxy, C 3 -C 30 arylthio, C 1 -C 30 alkylthio, C 2 -C 30 carbonyl, C 1 -C 30 carboxyl, amino, amido, or polyaryl;
R 14 and R 15 are independently H or substituted or unsubstituted C 1 -C 30 alkyl, C 2 -C 30 alkenyl, C 2 -C 30 alkynyl, C 3 -C 30 aryl, C 3 -C 30 heteroaryl, C 1 -C 30 alkoxy, C 3 -C 30 aryloxy, C 3 -C 30 arylthio, C 1 -C 30 alkylthio, C 2 -C 30 carbonyl, C 1 -C 30 carboxyl, amino, amido, or polyaryl; and
X − is an anion comprising chloride, nitrate, triflate, hexafluorophosphate, perchlorate, tetrafluoroborate, or tetraphenylboronate.

9. 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.

10. 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(vin

Assignees

• Univ Hong Kong

Inventors

• Yam Vivian Wing-Wah
• Zhang Kaka
• Leung Yu-Lut
• Yeung Margaret Ching-Lam
• Chan Kwun-Wa

Classifications

• C08K5/56 Primary

  Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond · CPC title

• D10B2331/06

  polyethers · CPC title

• D01F6/94

  of other polycondensation products · CPC title

• B82Y30/00

  Nanotechnology for materials or surface science, e.g. nanocomposites · CPC title

• D01F6/36

  comprising unsaturated carboxylic acids or unsaturated organic esters as the major constituent · CPC title