Mesoscopic materials comprised of ordered superlattices of microporous metal-organic frameworks

Patent metadata

Field	Value
Publication number	US-10494386-B2
Application number	US-201515126569-A
Country	US
Kind code	B2
Filing date	Mar 17, 2015
Priority date	Mar 18, 2014
Publication date	Dec 3, 2019
Grant date	Dec 3, 2019

Abstract

The disclosure provides for MOF heterolites comprised of ordered superlattices of MOFs, the manufacture thereof, and the use of the MOF heterolites for various applications, such as gas separation and/or storage, catalysis, light harvesting, and meta-materials.

First claim

What is claimed is:

1. A mesoscopic material that is comprised of an ordered superlattice of a plurality of two to eight structurally different nano- or micro-porous metal-organic framework (MOF) nanocrystals, wherein the ordered superlattice comprises interlocking well-organized nanocrystals, and wherein the mesoscopic material exhibits chemical and physical properties that result from the interplay between nanoscopic MOF building blocks at the mesoscopic level.

2. The mesoscopic material of claim 1 , wherein the plurality of MOF nanocrystals are comprised of a plurality of linked M-X-L units, wherein M is a metal, metal ion, or metal containing complex; X is an atom from an organic linking ligand that can form one or more bonds with M; and L is an organic linking ligand comprising an optionally substituted (C 1 -C 20 ) alkyl, optionally substituted (C 1 -C 20 ) alkenyl, optionally substituted (C 1 -C 20 ) alkynyl, optionally substituted (C 1 -C 20 ) hetero-alkyl, optionally substituted (C 1 -C 20 ) hetero-alkenyl, optionally substituted (C 1 -C 20 ) hetero-alkynyl, optionally substituted (C 3 -C 12 ) cycloalkyl, optionally substituted (C 3 -C 12 ) cycloalkenyl, optionally substituted aryl, optionally substituted heterocycle or optionally substituted mixed ring system, wherein the organic linking ligand comprises at least two or more carboxylate linking clusters.

3. The mesoscopic material of claim 2 , wherein the organic linking ligand is selected from the group consisting of:

wherein the carboxylate groups depicted in formulas I-XXXIII form a bond with a metal, metal ion or metal complex, and wherein,
A 1 -A 8 are independently a C, N, O, or S;
A 9 is selected from

X 1 -X 8 are independently selected from H, D, optionally substituted FG, optionally substituted (C 1 -C 20 )alkyl, optionally substituted (C 1 -C 19 )heteroalkyl, optionally substituted (C 1 -C 20 )alkenyl, optionally substituted (C 1 -C 19 )heteroalkenyl, optionally substituted (C 1 -C 19 )alkynyl, optionally substituted (C 1 -C 19 )heteroalkynyl, optionally substituted (C 1 -C 19 )cycloalkyl, optionally substituted (C 1 -C 19 )cycloalkenyl, optionally substituted aryl, optionally substituted heterocycle, and optionally substituted mixed ring system; and
R 1 -R 192 are independently selected from H, D, optionally substituted FG, optionally substituted (C 1 -C 20 )alkyl, optionally substituted (C 1 -C 19 )heteroalkyl, optionally substituted (C 1 -C 20 )alkenyl, optionally substituted (C 1 -C 19 )heteroalkenyl, optionally substituted (C 1 -C 19 )alkynyl, optionally substituted (C 1 -C 19 )heteroalkynyl, optionally substituted (C 1 -C 19 )cycloalkyl, optionally substituted (C 1 -C 19 )cycloalkenyl, optionally substituted aryl, optionally substituted heterocycle, and optionally substituted mixed ring system.

4. The mesoscopic material of claim 3 , wherein the organic linking ligand comprises a structured selected from the group consisting of:

wherein the carboxylate groups in Formula I, V, VII and XXIII undergo condensation with a metal, metal ion or metal complex, and wherein
A 1 -A 3 are independently a C, N, O, or S
X 1 -X 3 are independently selected from H, D, optionally substituted FG, optionally substituted (C 1 -C 20 )alkyl, optionally substituted (C 1 -C 19 )heteroalkyl, optionally substituted (C 1 -C 20 )alkenyl, optionally substituted (C 1 -C 19 )heteroalkenyl, optionally substituted (C 1 -C 19 )alkynyl, optionally substituted (C 1 -C 19 )heteroalkynyl, optionally substituted (C 1 -C 19 )cycloalkyl, optionally substituted (C 1 -C 19 )cycloalkenyl, optionally substituted aryl, optionally substituted heterocycle, and optionally substituted mixed ring system; and
R 37 -R 40 , R 47 -R 54 , R 187 -R 192 are independently selected from H, D, optionally substituted FG, optionally substituted (C 1 -C 20 )alkyl, optionally substituted (C 1 -C 19 )heteroalkyl, optionally substituted (C 1 -C 20 )alkenyl, optionally substituted (C 1 -C 19 )heteroalkenyl, optionally substituted (C 1 -C 19 )alkynyl, optionally substituted (C 1 -C 19 )heteroalkynyl, optionally substituted (C 1 -C 19 )cycloalkyl, optionally substituted (C 1 -C 19 )cycloalkenyl, optionally substituted aryl, and optionally substituted heterocycle, optionally substituted mixed ring system.

5. The mesoscopic material of claim 3 , wherein R 1 -R 192 are independently selected from:

6. The mesoscopic material of claim 2 , wherein M is a metal or metal ion selected from Li + , Na + , K + , Rb + , Cs + , Be 2+ , Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ , Sc 3+ , Sc 2+ , Sc + , Y 3+ , Y 2+ , Y + , Ti 4+ , Ti 3+ , Ti 2+ , Zr 4+ , Zr 3+ , Zr 2+ , Hf 4+ , Hf 3+ , V 5+ , V 4+ , V 3+ , V 2+ , Nb 5+ , Nb 4+ , Nb 3+ , Nb 2+ , Ta 5+ , Ta 4+ , Ta 3+ , Ta 2+ , Cr 6+ , Cr 5+ , Cr 4+ , Cr 3+ , Cr 2+ , Cr + , Cr, Mo 6+ , Mo 5+ , Mo 4+ , Mo 3+ , Mo 2+ , Mo + , Mo, W 6+ , W 5+ , W 4+ , W 3+ , W 2+ , W + , W, Mn 7+ , Mn 6+ , Mn 5+ , Mn 4+ , Mn 3+ , Mn 2+ , Mn + , Re 7+ , Re 6+ , Re 5+ , Re 4+ , Re 3+ , Re 2+ , Re + , Re, Fe 6+ , Fe 4+ , Fe 3+ , Fe 2+ , Fe + , Fe, Ru 8+ , Ru 7+ , Ru 6+ , Ru 4+ , Ru 3+ , Ru 2+ , Os 8+ , Os 7+ , Os 6+ , Os 5+ , Os 4+ , Os 3+ , Os 2+ , Os + , Os, Co 5+ , Co 4+ , Co 3+ , Co 2+ , Co + , Rh 6+ , Rh 5+ , Rh 4+ , Rh 3+ , Rh 2+ , Rh + , Ir 6+ , Ir 5+ , Ir 4+ , Ir 3+ , Ir 2+ , Ir + , Ir, Ni 3+ , Ni 2+ , Ni + , Ni, Pd 6+ , Pd 4+ , Pd 2+ , Pd + , Pd, Pt 6+ , Pt 5+ , Pt 4+ , Pt 3+ , Pt 2+ , Pt + , Cu 4+ , Cu 3+ , Cu 2+ , Cu + , Ag 3+ , Ag 2+ , Ag + , Au 5+ , Au 4+ , Au 3+ , Au 2+ , Au + , Zn 2+ , Zn + , Zn, Cd 2+ , Cd + , Hg 4+ , Hg 2+ , Hg + , B 3+ , B 2+ , B + , Al 3+ , Al 2+ , Al + , Ga 3+ , Ga 2+ , Ga + , In 3+ , In 2+ , In 1+ , Tl 3+ , Tl + , Si 4+ , Si 3+ , Si 2+ , Si + , Ge 4+ , Ge 3+ , Ge 2+ , Ge + , Ge, Sn 4+ , Sn 2+ , Pb 4+ , Pb 2+ , As 5+ , As 3+ , As 2+ , As + , Sb 5+ , Sb 3+ , Bi 5+ , Bi 3+ , Te 6+ , Te 5+ , Te 4+ , Te 2+ , La 3+ , La 2+ , Ce 4+ , Ce 3+ , Ce 2+ , Pr 4+ , Pr 3+ , Pr 2+ , Nd 3+ , Nd 2+ , Sm 3+ , Sm 2+ , Eu 3+ , Eu 2+ , Gd 3+ , Gd 2+ , Gd + , Tb 4+ , Tb 3+ , Tb 2+ , Tb + , Db 3+ , Db 2+ , Ho 3+ , Er 3+ , Tm 4+ , Tm 3+ , Tm 2+ , Yb 3+ , Yb 2+ , Lu 3+ , and combinations thereof, including any complexes which contain the metals or metal ions listed above, as well as any corresponding metal salt counter-anions.

7. The mesoscopic material of claim 1 , wherein the ordered superlattice is comprised of a plurality of zirconium based MOF nanocrystals.

8. The mesoscopic material of claim 1 , wherein the ordered superlattice is comprised of homogeneous MOF nanocrystals.

9. The mesoscopic material of claim 1 , wherein the ordered superlattice is comprised of heterogeneous MOF nanocrystals.

10. The mesoscopic material of claim 1 , wherein the structurally different MOFs have different gas sorption and/or gas separation properties.

11. The mesoscopic material of claim 1 , wherein the structurally different MOFs ha

Assignees

• Univ California

Inventors

• Yaghi Omar M
• Choi Kyungmin

Classifications

• B01D2257/504

  Carbon dioxide · CPC title

• B01D2257/406

  Ammonia · CPC title

• B01D2257/306

  Organic sulfur compounds, e.g. mercaptans · CPC title

• B01J31/123

  Organometallic polymers, e.g. comprising C-Si bonds in the main chain or in subunits grafted to the main chain (B01J31/064, B01J31/066, B01J31/067, B01J31/08 and B01J31/10 take precedence; polymer-bound organometallic complexes B01J31/165; coordination polymers B01J31/1691; catalysts for the preparation of polysiloxanes, e.g. Karstedt catalysts C08G77/08) · CPC title

• B01D2257/402

  Dinitrogen oxide · CPC title