# US 10,766,911 B2 · Coordinative alignment of molecules in chiral metal-organic frameworks

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- Number: US 10,766,911 B2
- Document ID: US10766911B2
- Status: Granted
- Kind: B2
- Application number: 16/270,666
- Filed: 2019-02-08
- Published: 2019-06-06
- Granted: 2020-09-08
- Earliest claimed: 2016-08-09
- Assignees: The Regents of the University of California
- Applicants: The Regents of the University of California
- Inventors: Seungkyu Lee; Eugene A. Kapustin; Omar M. Yaghi
- Web page: https://patentgrep.com/patent/US10766911B2

## CPC

- C07F 5/069: {without C-aluminium linkages}
- B01D 53/04: with stationary adsorbents {(B01D53/025 takes precedence)}
- B01J 20/226: {Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF] (preparation of metal complexes containing carboxylic acid moieties C07C51/418; MOF's per se C07F)}
- G01N 23/2202: Preparing specimens therefor
- C07B 2200/07: Optical isomers
- C07B 2200/13: Crystalline forms, e.g. polymorphs
- C07F: ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM (metal-containing porphyrins C07D487/22)
- B01D: SEPARATION (separating solids from solids by wet methods B03B, B03D; by pneumatic jigs or tables B03B; by other dry methods B07; magnetic or electrostatic separation of solid materials from solid materials or fluids, separation by high-voltage electric fields B03C; centrifuges, vortex apparatus B04; presses per se for squeezing-out liquid from liquid-containing material B30B9/02; treatment of water C02F, e.g. softening by ion-exchange C02F1/42; {arrangements of air intake cleaners in gas turbine plants F02C7/05} ; arrangements or mounting of filters in air-conditioning, air-humidification or ventilation F24F13/28)
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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)
- C07B: GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR (preparation of carboxylic acid esters by telomerisation C07C67/47; telomerisation C08F)

## Abstract

Coordinative alignment uses x-ray diffraction to precisely and unambiguously determine the structure of molecules bound or crystallized within chiral metal organic frameworks.

## Claims

### Claim 1

A method of coordinative alignment (CAL) to determine the structure of target molecules, comprising coordinative aligning and crystalizing the target molecules within a chiral metal organic framework (MOF), wherein:
(i) the target molecules bind to the interior of the MOF through covalent and/or ionic bonds, and are oriented in pores of the MOF such that reduced vibrations and restricted orientations by the bonds enable structural determination of the oriented target molecules by diffraction methods like single crystal x-ray diffraction;
(ii) chiral symmetry of the MOF serves as a reference for determining the absolute configuration of the bound target molecules, such that the chiral environment of the pore enables enantioselective crystallization of the target molecules in the pores, which can be applied to crystallize one enantiomer from a recemic mixture;
(iii) the MOF provides sufficiently large single crystals so that the crystals diffract enough for the structure determination, and functionalities that can interact with incoming molecules, including open metal sites and organic functional groups, sufficient to make the covalent and/or ionic bonds with incoming target molecules; and
(iv) the target molecules are chiral, are of size to be bound within the pores of the MOF, and comprise organic functional groups sufficient to make the covalent and/or ionic bonds with the MOF,
wherein the functional groups of the target molecules are selected from carboxylic acid, primary alcohol, and phenol.

### Claim 2 (depends on 1)

The method of claim 1 wherein the MOF is selected from:
a) MOF-74, MOF-808, PCN-700, MOF-545, and MOF-535;
b) chiral MOF-5 and MOFs based on mandelate; and
c) MOF-520, Al8(μ-OH)8(HCOO)4(BTB)4, (BTB=1,3,5-benzenetribenzoate).

### Claim 3 (depends on 1)

The method of claim 1 wherein the MOF is MOF-520, Al8(μ-OH)8(HCOO)4(BTB)4, (BTB=1,3,5-benzenetribenzoate).

### Claim 4 (depends on 1)

The method of claim 1 wherein the MOF is MOF-520, Al8(μ-OH)8(HCOO)4(BTB)4, (BTB=1,3,5-benzenetribenzoate), the functional groups of the target molecules are carboxylic acid, and the target molecules are gibberellin form A1.

### Claim 5

A method of coordinative alignment (CAL) to determine the structure of target molecules, comprising coordinative aligning and crystalizing the target molecules within a chiral metal organic framework (MOF), wherein:
(i) the target molecules bind to the interior of the MOF through covalent and/or ionic bonds, and are oriented in pores of the MOF such that reduced vibrations and restricted orientations by the bonds enable structural determination of the oriented target molecules by diffraction methods like single crystal x-ray diffraction;
(ii) chiral symmetry of the MOF serves as a reference for determining the absolute configuration of the bound target molecules, such that the chiral environment of the pore enables enantioselective crystallization of the target molecules in the pores, which can be applied to crystallize one enantiomer from a recemic mixture;
(iii) the MOF provides sufficiently large single crystals so that the crystals diffract enough for the structure determination, and functionalities that can interact with incoming molecules, including open metal sites and organic functional groups, sufficient to make the covalent and/or ionic bonds with incoming target molecules; and
(iv) the target molecules are chiral, are of size to be bound within the pores of the MOF, and comprise organic functional groups sufficient to make the covalent and/or ionic bonds with the MOF,
wherein the target molecules are selected from: benzoic acid, methanol, ethylene glycol, 3-nitrophenol, heptanoic acid, 3-hydroxybenzoic acid, 3,5-diaminobenzoic acid, trimesic acid, 4-bromophenol, 2-(2,6-dichloranilino)phenylacetic acid (diclofenac), 5,7-dihydroxy-3-(4-hydroxyphenyl)chromen-4-one (genistein), tert-butyloxycarbonyl-(RS)-3-amino-1,2-propanediol, gibberellin form A1 and A3, and (±)-jasmonic acid.

### Claim 6 (depends on 5)

The method of claim 5 wherein the MOF is selected from:
a) MOF-74, MOF-808, PCN-700, MOF-545, and MOF-535;
b) chiral MOF-5 and MOFs based on mandelate; and
c) MOF-520, Al8(μ-OH)8(HCOO)4(BTB)4, (BTB=1,3,5-benzenetribenzoate).

### Claim 7 (depends on 5)

The method of claim 5 wherein the MOF is MOF-520, Al8(μ-OH)8(HCOO)4(BTB)4, (BTB=1,3,5-benzenetribenzoate).

### Claim 8

A method of coordinative alignment (CAL) to determine the structure of target molecules, comprising coordinative aligning and crystalizing the target molecules within a chiral metal organic framework (MOF), wherein:
(i) the target molecules bind to the interior of the MOF through covalent and/or ionic bonds, and are oriented in pores of the MOF such that reduced vibrations and restricted orientations by the bonds enable structural determination of the oriented target molecules by diffraction methods like single crystal x-ray diffraction;
(ii) chiral symmetry of the MOF serves as a reference for determining the absolute configuration of the bound target molecules, such that the chiral environment of the pore enables enantioselective crystallization of the target molecules in the pores, which can be applied to crystallize one enantiomer from a recemic mixture;
(iii) the MOF provides sufficiently large single crystals so that the crystals diffract enough for the structure determination, and functionalities that can interact with incoming molecules, including open metal sites and organic functional groups, sufficient to make the covalent and/or ionic bonds with incoming target molecules; and
(iv) the target molecules are chiral, are of size to be bound within the pores of the MOF, and comprise organic functional groups sufficient to make the covalent and/or ionic bonds with the MOF,
wherein the MOF is selected from:
a) MOF-74, MOF-808, PCN-700, MOF-545, and MOF-535;
b) chiral MOF-5 and MOFs based on mandelate; and
c) MOF-520, Al8(μ-OH)8(HCOO)4(BTB)4, (BTB=1,3,5-benzenetribenzoate).

### Claim 9 (depends on 8)

The method of claim 8 wherein the MOF is MOF-520, Al8(μ-OH)8(HCOO)4(BTB)4, (BTB=1,3,5-benzenetribenzoate).