WO2015157239A1

WO2015157239A1 - Functionalized and multivariate btb-based metal organic frameworks

Info

Publication number: WO2015157239A1
Application number: PCT/US2015/024651
Authority: WO
Inventors: Omar M. Yaghi; Yuebiao ZHANG; Hexiang Deng
Original assignee: The Regents Of The University Of California
Priority date: 2014-04-07
Filing date: 2015-04-07
Publication date: 2015-10-15

Abstract

The disclosure provides for metal organic frameworks (MOFs) which comprise a plurality of SBUs linked together by functionalized or multivariate BTB-based linking ligands. The disclosure further provides for the use of these MOFs in variety of applications, including for gas separation, gas storage, catalysis, and separation of compounds or bioproducts.

Description

FUNCTIONALIZED AND MULTIVARIATE BTB-BASED METAL ORGANIC

FRAMEWORKS

CROSS REFERENCE TO RELATED APPLICATIONS

[0001] This application claims priority under 35 U.S.C. §119 from Provisional Application Serial No. 61/976,462, filed April 7, 2014, the disclosure of which is incorporated herein by reference.

TECHNICAL FIELD

[0002] The disclosure provides for metal organic frameworks (MOFs) which comprise a plurality of SBUs linked together by functionalized and/or multivariate BTB-based linking ligands. The disclosure further provides for the use of these MOFs in variety of

applications, including for gas separation, gas storage, catalysis, and separation of compounds or bioproducts .

BACKGROUND

[0003] Metal-organic frameworks (MOFs) are porous crystalline materials that are constructed by linking metal clusters called Secondary Binding Units (SBUs) together with organic linking ligands. MOFs have high surface area and high porosity which enable them to be utilized in diverse fields, such as gas storage, catalysis, and sensors.

SUMMARY

[0004] The disclosure provides for MOFs which comprise a plurality of SBUs linked together by a plurality of functionalized 1,3,5- tris (4-carboxyphenyl) benzene (BTB) -based linking ligands. The disclosure also provides for a MOF disclosed herein being

multivariate by being comprised of two or more differently

functionalized BTB-based linking ligands (e.g., BTB and BTB-N0₂) .

The material properties of the multivariate (mtv) -MOFs can be readily modified by changing the ratio of different types of organic linking ligands. A MOF of the disclosure may be topologically uniform (e.g., qom, rtl, or pyr net), while not being uniform in terms of the linking ligands all having the same structure. The structural tunability of the MOFs of the disclosure therefore allows for fine-tuning of the structural properties of the frameworks.

Thus, MOFs can be synthesized to have certain properties and functionality in order to meet intended applications, such as for gas, liquid or vapor separation, gas storage, separation of bioproducts or compounds, or catalysis. In particular, it has been found that the MOFs of the disclosure have improved hydrogen and methane gas uptake in comparison to MOF-177 and other BTB-based frameworks. Accordingly, the MOFs of the disclosure are ideally suited for use as fuel gas storage materials in Absorbed Natural Gas

(ANG) tanks, cylinders or the like for powering vehicles.

[0005] In a particular embodiment, the disclosure provides for a metal organic framework (MOF) which comprises a plurality SBUs that are linked together by a plurality of 1, 3, 5-tris (4- carboxyphenyl ) benzene (BTB) -based linking ligands comprising the structure of Formula I :

Formula (I)

wherein, A¹-A³ are independently a C or N; R^x-R¹² are independently selected from H, D, FG, optionally substituted (C1-C12) alkyl, optionally substituted hetero- (C1-C12) alkyl, optionally substituted (C1-C12) alkenyl, optionally substituted hetero- (C1-C12) alkenyl, optionally substituted (C1-C12) alkynyl, optionally substituted hetero- (Ci- C12) alkynyl, optionally substituted (C1-C12 ) cycloalkyl , optionally substituted (C1-C12) cycloalkenyl , optionally substituted aryl, optionally substituted heterocycle, optionally substituted mixed ring system, -C(R¹³)₃, -CH(R¹³)₂, -CH₂R¹³, -C(R¹⁴)₃, -CH(R¹⁴)₂, - CH₂R¹⁴, -OC(R¹³)₃, OCH(R¹³)₂, -OCH2R¹³, -OC(R¹⁴)₃, -OCH(R¹⁴)₂, OCH₂R¹⁴, wherein R^x-R¹² when adjacent can be linked together to form one or more optionally substituted rings selected from the group comprising cycloalkyl, cycloalkenyl, heterocycle, aryl, and mixed ring system; R¹³ is selected from FG, optionally substituted (C1-C12) alkyl, optionally substituted hetero- (C1-C12) alkyl, optionally substituted (C1-C12) alkenyl, optionally substituted hetero- (C1-C12) alkenyl, optionally substituted (C1-C12) alkynyl, optionally substituted hetero- (Ci- C12) alkynyl, hemiacetal, hemiketal, acetal, ketal, and orthoester; R¹⁴ is selected from one or more substituted or unsubstituted rings selected from cycloalkyl, aryl and heterocycle ; and wherein when A¹-A³ are C and R^x-R¹² are H, the MOF further comprises a functionalized BTB-based linking ligand having the structure of Formula I, where at least one of R^x-R¹² is not H. In a further embodiment R^x-R¹² are inde endentl selected from



and M is an alkaline metal species, an alkaline-earth metal species, or transition metal species that has a formal charge of +1 and that can be coordinated by one or more neutral or charged ligands. In yet a further embodiment, the BTB-based linking ligand comprises the structure of:



and

[0006] In a particular embodiment, a MOF disclosed herein is multivariate by comprising two or more BTB-based linking ligands comprising the structure of Formula I :

Formula (I) wherein,

A¹-A³ are independently a C or N;

R^x-R¹² are independently selected from H, D, FG, optionally substituted (C1-C12) alkyl, optionally substituted hetero- (Ci- Ci2)alkyl, optionally substituted (C1-C12) alkenyl, optionally substituted hetero- (C1-C12) alkenyl, optionally substituted (Ci- Ci2)alkynyl, optionally substituted hetero- (Ci- Ci2)alkynyl,

optionally substituted (C1-C12) cycloalkyl, optionally substituted (C1-C12) cycloalkenyl, optionally substituted aryl, optionally substituted heterocycle, optionally substituted mixed ring system, - C(R¹³)₃, -CH(R¹³)₂, -CH2R¹³, -C(R¹⁴)₃, -CH(R¹⁴)₂, -CH₂R¹⁴, -OC(R¹³)₃, OCH(R¹³)₂, -OCH2R¹³, -OC(R¹⁴)₃, -OCH(R¹⁴)₂, OCH₂R¹⁴, wherein R^x-R¹² when adjacent can be linked together to form one or more optionally substituted rings selected from the group comprising cycloalkyl, cycloalkenyl, heterocycle, aryl, and mixed ring system; R¹³ is selected from FG, optionally substituted (C1-C12) alkyl, optionally substituted hetero- (C1-C12) alkyl, optionally substituted (Ci- C12) alkenyl, optionally substituted hetero- (C1-C12) alkenyl, optionally substituted (C1-C12) alkynyl, optionally substituted hetero- (Ci- C12) alkynyl, hemiacetal, hemiketal, acetal, ketal, and orthoester; R¹⁴ is selected from one or more substituted or unsubstituted rings selected from cycloalkyl, aryl and heterocycle; and wherein the MOF comprises two or more linking ligands which have different

structures .

[0007] In a further embodiment, wherein the two or more BTB-based linking ligands are selected from:

[ 0008 ] In a particular embodiment, a MOF of the disclosure comprises a plurality of SBUs which comprise one or more metals or metal ions selected from: Li⁺, Na⁺, K⁺, Rb⁺, Cs⁺, Be²⁺, Mg²⁺, Ca²⁺,

Ba²⁺, Sc³⁺, Sc²⁺, Sc\ Y³⁺, Y²⁺, Y⁺, Ti⁴⁺, Ti³⁺, Ti²⁺, Zr⁴⁺, Zr³⁺, Zr²⁺,

Hf⁴⁺, Hf³⁺, V⁵⁺, V⁴⁺, V³⁺, V²⁺, Nb⁵⁺, Nb⁴⁺, Nb³⁺, Nb²⁺, Ta⁵⁺, Ta⁴⁺, Ta³⁺,

Ta²⁺, Cr⁶⁺, Cr⁵⁺, Cr⁴⁺, Cr³⁺, Cr²⁺, Cr⁺, Cr, Mo ⁶⁺, Mo ⁵⁺, Mo ⁴⁺, Mo ³⁺, Mo

Mo⁺, Mo, W⁶⁺, W ⁵⁺, W⁴⁺, W³⁺ , w²⁺, w⁺, w , Mn⁷⁺ , Mn⁶⁺, Mn⁵⁺, Mn⁴⁺, Mn³⁺, Mn²⁺,

Mn⁺, Re⁷⁺, Re⁶⁺, Re⁵⁺ , Re⁴⁺ , Re³⁺, Re²⁺, . Re⁺, Re, Fe⁶⁺, Fe⁴⁺, Fe³⁺, Fe²⁺,

Fe⁺, Fe, Ru⁸⁺, Ru⁷⁺, Ru⁶⁺, Ru⁴⁺, Ru³⁺, Ru²⁺, Os⁸⁺, Os⁷⁺, Os⁶⁺, Os⁵⁺, Os⁴⁺,

Os³⁺, Os²⁺, Os⁺, Os, Co⁵⁺, Co⁴⁺, Co³⁺, Co²⁺, Co⁺, Rh⁶⁺, Rh⁵⁺, Rh⁴⁺, Rh³⁺,

Rh²⁺, Rh⁺, Ir⁶⁺, _jr5+ , Ir⁴⁺ , lr³⁺, Ir²⁺, T r⁺ Ir, Ni³⁺, Ni²⁺, Ni⁺, Ni, Pd⁶⁺,

Pd⁴⁺, Pd²⁺, Pd⁺, Pd, Pt⁶⁺, Pt⁵⁺, Pt⁴⁺, Pt³⁺, Pt²⁺, Pt⁺, Cu⁴⁺, Cu³⁺, Cu²⁺,

Cu⁺, Ag³⁺, Ag²⁺, Ag⁺, Au⁵⁺, Au⁴⁺, Au³⁺, Au²⁺, Au⁺, Zn²⁺, Zn⁺, Zn, Cd²⁺, Cd⁺,

Hg⁴⁺, Hg²⁺, Hg⁺, B³⁺, B²⁺, B⁺, Al^: ³⁺, Al ²⁺, Al ⁺, Ga ³⁺, Ga ²⁺, Ga ⁺, In³⁺, In²⁺,

In¹⁺, Tl³⁺, Tl⁺, Si⁴⁺ , Si³⁺ , Si²⁺, Si⁺, Ge⁴⁺, Ge³⁺, . Ge²⁺, , Ge⁺, Ge, Sn⁴⁺, Sn²⁺, Pb⁴⁺, Pb²⁺, As⁵⁺, As³⁺, As²⁺, As⁺, Sb⁵⁺, Sb³⁺, Bi⁵⁺, Bi³⁺, Te⁶⁺, Te⁵⁺,

Te⁴⁺, Te²⁺, La³⁺, La²⁺, Ce⁴⁺, Ce³⁺, Ce²⁺, Pr⁴⁺, Pr³⁺, p_r2 + , Nd³⁺, Nd²⁺, Sm³⁺,

Sm²⁺, Eu³⁺, Eu²⁺, Gd³⁺, Gd²⁺, Gd⁺, Tb⁴⁺, Tb³⁺, Tb²⁺, Tb⁺, Db³⁺, Db²⁺, Ho³⁺,

Er³⁺, Tm⁴⁺, Tm³⁺, Tm²⁺, Yb³⁺, Yb²⁺, Lu³⁺, La³⁺, La²⁺, La⁺, and combinations thereof, including any complexes which contain the metals or metal ions, as well as any corresponding metal salt counter-anions . In another embodiment, the plurality of SBUs comprise zinc metal ions, including any complexes which contain the zinc metal ions, as well as any corresponding metal salt counter-anions. In yet another embodiment, a MOF of the disclosure comprises a qom, pyr or rtl net topology .

[ 0009 ] In a particular embodiment, the disclosure also provides for a device comprising a MOF disclosed herein. In a further embodiment, the device is a gas separation and/or gas storage device. In yet a further embodiment the device is Absorbed Natural Gas (ANG) tank and comprises the MOF as an adsorbent. In another certain embodiment, the disclosure provides for a vehicle which comprises the ANG tank device .

[ 0010 ] In a certain embodiment, the disclosure provides a method of separating and/or storing one or more gases from a gas mixture comprising contacting the gas mixture with a MOF of the disclosure. In a further embodiment, the gas mixture is natural gas and the gas that is separated and/or stored is methane. In an alternate embodiment, the gas mixture comprises hydrogen and the gas that is separated and/or stored is hydrogen.

DESCRIPTION OF DRAWINGS

[ 0011 ] Figure 1 diagrams the reticular synthesis of MOF-177 by linking octahedral and triangle SUBs to form a hetero (6,3)- coordinated qom net.

[ 0012 ] Figure 2A-M illustrates 1, 3, 5-tris (4- carboxyphenyl ) benzene (BTB) -based linkers for the functionalized and multivariate MOF of the disclosure. Abbreviations: (A) H₃BTB, 1,3,5- tris (4-carboxyphenyl) benzene; (B) H3BTB-NH2 , 1, 3, 5-tris (3-amino-4- carboxyphenyl ) benzene ; (C) H3BTB-NO2 , 1, 3, 5-tris (3-nitro-4- carboxyphenyl ) benzene ; (D) IH BTB-OMe, 1, 3, 5-tris (3-methoxy-4- carboxyphenyl ) benzene ; (E) IH BTB-OBn, 1, 3, 5-tris (3-benzyloxy-4- carboxyphenyl ) benzene ; (F) H3BTB- 6 F , 1, 3, 5-tris (3, 5-difluoro-4- carboxyphenyl ) benzene ; (G) IH BTB-Nap, 1, 3, 5-tris (4- carboxynaphthalen-l-yl) benzene; (H) H3BTB- 3 F , 1, 3, 5-tris (3-fluoro-4- carboxyphenyl ) benzene ; (I) H3BTB-3Me, 1, 3, 5-tris (3-methyl-4- carboxyphenyl ) benzene ; (J) IH BTB-mNlH , 1, 3, 5-tris (2-amino-4- carboxyphenyl ) benzene ; (K) IH BTB-Nap-NlH , 1- (3-amino-4- carboxyphenyl ) -3- ( 4-carboxyphenyl ) -5- (4-carboxynaphthalen-l-yl) - benzene; and (L) H₃BTB- 6F , 1, 3, 5-tris (3, 5-dimethyl-4- carboxyphenyl ) benzene . (M) BTB Linkers with Various Functional Groups at Selected Positions and the Corresponding MOFs Formed from Either Pure Linker or Mixing of Various Linkers (A = H3BTB; B = H3BTB-NH2, 1, 3, 5-tris (3-amino-4-carboxyphenyl) benzene; C = H3BTB- N02, 1, 3, 5-tris (3-nitro-4-carboxyphenyl) benzene; D = H3BTB-OCH3 , 1, 3, 5-tris (3-methoxy-4-carboxyphenyl) benzene; E = H3BTB-OC7H7, 1, 3, 5-tris (3-benzyloxy-4-carboxyphenyl) benzene; F = H3BTBF2, 1,3,5- tris (3, 5-difluoro-4-carboxyphenyl) benzene; G = H3BTB-C4H4, 1,3,5- tris (4-carboxy-naphthalen-l-yl) benzene; H = H3BTB-F, 1 , 3 , 5-tris ( 3- fluoro-4-carboxyphenyl) benzene; I = H3BTB-CH3, 1 , 3, 5-tris (3-methyl- 4-carboxyphenyl) benzene; J = H3BTB-mNH2, 1, 3, 5-tris (2-amino-4- carboxyphenyl) benzene; K = H3BTB-C4H4 /NH2 , 1- (3-amino-4- carboxyphenyl ) -3- (4-carboxyphenyl) -5- (4-carboxynaphthalen-l-yl) - benzene .

[ 0013 ] Figure 3A-I illustrates the crystal structures of MOFs comprising BTB-based linking moieties. Abbreviations: (A) IRMOF- 177-B, H3BTB-NH2 linking ligands and Zn₄0(-COO)₆ SBUs . (B) IRMOF-177- D, H₃BTB-OMe linking ligands and Zn₄0(-COO)₆ SBUs; (C) IRMOF-177-E, H₃BTB-OBn linking ligands and Zn₄0(-COO)₆ SBUs; (D) IRMOF-177-F, H3BTB- 6 F linking ligands and Zn₄0(-COO)₆ SBUs; (E) IRMOF-177-G, H₃BTB-Nap linking ligands and Zn₄0(-COO)₆ SBUs; (F) IRMOF-177-H, H₃BTB-3F linking ligands and Zn₄0(-COO)₆ SBUs; (G) IRMOF-177-I, H₃BTB-3Me linking ligands and Zn₄0(-COO)₆ SBUs; (H) IRMOF-177-J, H₃BTB-mNH₂ linking ligands and Zn₄0(-COO)₆ SBUs; and (I) IRMOF-177-K, H₃BTB-Nap-NH₂ linking ligands and Zn₄0(-COO)₆ SBUs.

[ 0014 ] Figure 4A-C illustrates (A) the crystal structure of a topological isomer to MOF-177-F with a pyr net. (B) - (C) Crystal structure of MOF-155-F made from linker F in doubly interpenetrated pyr net (B) and crystal structure of MOF-156-J made from linker J forming the rtl net (C) . The interpenetrating framework (hexagons linked by polyhedral) in (B) is also depicted. The large sphere represents the void in the structure.

[ 0015 ] Figure 5 illustrates several possible MOF topological nets that can result by alternatively linking octahedrons and triangles .

[ 0016] Figure 6 illustrates the crystal structure of a

topological isomer MOF to MOF-177-J with rtl net.

[ 0017 ] Figure 7A-B illustrates (A) structure of MTV-MOF-177-

F(l:l) and (B) the input-output relation at different temperatures (75 and 85 °C) .

[ 0018 ] Figure 8 provides a ID solution ¹H NMR spectrum of MTV- MOF-177-ABG for output linker ratio characterization.

[ 0019 ] Figure 9 provides the powder X-ray diffraction (PXRD) pattern of synthesized IRMOF-177-B as compared with the simulated pattern for IRMOF-177-B.

[ 0020 ] Figure 10 provides the PXRD pattern of synthesized multivariate IRMOF-177-AC as compared with the simulated pattern for IRMOF-177-AC .

[ 0021 ] Figure 11 provides the PXRD pattern of synthesized IRMOF- 177-D as compared with the simulated pattern for IRMOF-177-D.

[ 0022 ] Figure 12 provides the PXRD pattern of synthesized IRMOF- 177-E as compared with the simulated pattern for IRMOF-177-E.

[ 0023 ] Figure 13 provides the PXRD pattern of synthesized multivariate IRMOF-177-AF as compared with the simulated pattern for IRMOF-177.

[ 0024 ] Figure 14 provides the PXRD pattern of synthesized IRMOF- 177-G as compared with the simulated pattern for IRMOF-177-G.

[ 0025 ] Figure 15A-B presents N2 (Ar) adsorption isotherms at 77

K (87 K) for MOF-177 analogues (A) and MTV-MOF-177 derivatives (B) , showing that all MOFs have permanent porosity and high surface area after activation.

[ 0026] Figure 16A-B presents (A) nitrogen and (B) hydrogen adsorption isotherms for multivariate MOF-177-AF with the

stoichiometry of 5:5 and 3:7 coupling with MOF-177 and MOF-177F.

[ 0027 ] Figure 17 presents methane adsorption isotherms for multivariate MOF-177 at 298 K. [ 0028 ] Figure 18 is a diagram demonstrating the relationship between input ratios and output ratios of various functionalized linkers in MTVMOF-177-AB, -AC, -AF, and -AG, respectively. As the input ratio increases, the presence of linker in the MTV-MOF backbone also increases, albeit in a nonlinear relationship.

[ 0029 ] Figure 19A-B shows volumetric H₂ uptake at 77 K for MOF-177- X (A) and MTV-MOF-177 compounds (B) . A maximum 25% increase of H₂ uptake can be observed with MOF-177-B and -D, when -N¾ and -OCH3 functional groups are introduced, respectively.

[ 0030 ] Figure 20 shows volumetric CH₄ total uptake at 298 K for MTV-MOF-177-AF1 compared with those of the MOF-177-A and the bulk methane .

DETAILED DESCRIPTION

[ 0031 ] As used herein and in the appended claims, the singular forms "a, " "and, " and "the" include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to "an organic linking ligand" includes a plurality of such linking ligands and reference to "the metal ion" includes reference to one or more metal ions and equivalents thereof known to those skilled in the art, and so forth.

[ 0032 ] Also, the use of "or" means "and/or" unless stated otherwise. Similarly, "comprise," "comprises," "comprising"

"include, " "includes, " and "including" are interchangeable and not intended to be limiting.

[ 0033 ] It is to be further understood that where descriptions of various embodiments use the term "comprising, " those skilled in the art would understand that in some specific instances, an embodiment can be alternatively described using language "consisting

essentially of" or "consisting of."

[ 0034 ] All publications mentioned throughout the disclosure are incorporated herein by reference in full for the purpose of describing and disclosing the methodologies, which are described in the publications, which might be used in connection with the description herein. The publications discussed above and throughout the text are provided solely for their disclosure prior to the filing date of the present application. Nothing herein is to be construed as an admission that the inventors are not entitled to antedate such disclosure by virtue of prior disclosure. Moreover, with respect to similar or identical terms found in the incorporated references and terms expressly defined in this disclosure, the term definitions provided in this disclosure will control in all respects .

[0035] Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood to one of ordinary skill in the art. Although there are many methods and reagents similar or equivalent to those described herein, the exemplary methods and materials are presented herein.

[0036] As used herein, a wavy line intersecting another line that is connected to an atom indicates that this atom is covalently bonded to another entity that is present but not being depicted in the structure. A wavy line that does not intersect a line but is connected to an atom indicates that this atom is interacting with another atom by a bond or some other type of identifiable

association .

[0037] A bond indicated by a straight line and a dashed line indicates a bond that may be a single covalent bond or alternatively a double covalent bond. But in the case where an atom's maximum valence would be exceeded by forming a double covalent bond, then the bond would be a single covalent bond.

[0038] The term "alkyl", refers to an organic group that is comprised of carbon and hydrogen atoms that contain single covalent bonds between carbons. Typically, an "alkyl" as used in this disclosure, refers to an organic group that contains 1 to 30 carbon atoms, unless stated otherwise. Where if there is more than 1 carbon, the carbons may be connected in a linear manner, or alternatively if there are more than 2 carbons then the carbons may also be linked in a branched fashion so that the parent chain contains one or more secondary, tertiary, or quaternary carbons. An alkyl may be substituted or unsubstituted, unless stated otherwise.

[0039] The term "alkenyl", refers to an organic group that is comprised of carbon and hydrogen atoms that contains at least one double covalent bond between two carbons. Typically, an "alkenyl" as used in this disclosure, refers to organic group that contains 1 to 30 carbon atoms, unless stated otherwise. While a Ci-alkenyl can form a double bond to a carbon of a parent chain, an alkenyl group of three or more carbons can contain more than one double bond. It certain instances the alkenyl group will be conjugated, in other cases an alkenyl group will not be conjugated, and yet other cases the alkenyl group may have stretches of conjugation and stretches of nonconj ugation . Additionally, if there is more than 1 carbon, the carbons may be connected in a linear manner, or alternatively if there are more than 3 carbons then the carbons may also be linked in a branched fashion so that the parent chain contains one or more secondary, tertiary, or quaternary carbons. An alkenyl may be substituted or unsubstituted, unless stated otherwise.

[ 0040 ] The term "alkynyl", refers to an organic group that is comprised of carbon and hydrogen atoms that contains a triple covalent bond between two carbons. Typically, an "alkynyl" as used in this disclosure, refers to organic group that contains 1 to 30 carbon atoms, unless stated otherwise. While a Ci-alkynyl can form a triple bond to a carbon of a parent chain, an alkynyl group of three or more carbons can contain more than one triple bond. Where if there is more than 1 carbon, the carbons may be connected in a linear manner, or alternatively if there are more than 4 carbons then the carbons may also be linked in a branched fashion so that the parent chain contains one or more secondary, tertiary, or quaternary carbons. An alkynyl may be substituted or unsubstituted, unless stated otherwise.

[ 0041 ] The term "aryl", as used in this disclosure, refers to a conjugated planar ring system with delocalized pi electron clouds that contain only carbon as ring atoms. An "aryl" for the purposes of this disclosure encompass from 1 to 12 aryl rings wherein when the aryl is greater than 1 ring the aryl rings are joined so that they are linked, fused, or a combination thereof. An aryl may be substituted or unsubstituted, or in the case of more than one aryl ring, one or more rings may be unsubstituted, one or more rings may be substituted, or a combination thereof.

[ 0042 ] The term "cluster" refers to identifiable associations of

2 or more atoms. Such associations are typically established by some type of bond-ionic, covalent, Van der Waal, coordinate and the like. [ 0043 ] The term "cycloalkyl", as used in this disclosure, refers to an alkyl that contains at least 3 carbon atoms but no more than 12 carbon atoms connected so that it forms a ring. A "cycloalkyl" for the purposes of this disclosure encompass from 1 to 12

cycloalkyl rings, wherein when the cycloalkyl is greater than 1 ring, then the cycloalkyl rings are joined so that they are linked, fused, or a combination thereof. A cycloalkyl may be substituted or unsubstituted, or in the case of more than one cycloalkyl ring, one or more rings may be unsubstituted, one or more rings may be substituted, or a combination thereof.

[ 0044 ] The term "cycloalkenyl" , as used in this disclosure, refers to an alkene that contains at least 3 carbon atoms but no more than 12 carbon atoms connected so that it forms a ring. A "cycloalkenyl" for the purposes of this disclosure encompass from 1 to 12 cycloalkenyl rings, wherein when the cycloalkenyl is greater than 1 ring, then the cycloalkenyl rings are joined so that they are linked, fused, or a combination thereof. A cycloalkenyl may be substituted or unsubstituted, or in the case of more than one cycloalkenyl ring, one or more rings may be unsubstituted, one or more rings may be substituted, or a combination thereof.

[ 0045 ] The term "framework" as used herein, refers to a highly ordered structure comprised of secondary building units (SBUs) that can be linked together in defined, repeated and controllable manner, such that the resulting structure is characterized as being porous, periodic and crystalline. Typically, "frameworks" are two

dimensional (2D) or three dimensional (3D) structures. Examples of "frameworks" include, but are not limited to, "metal-organic frameworks" or "MOFs", "zeolitic imidazolate frameworks" or "ZIFs", or "covalent organic frameworks " or "COFs". While MOFs and ZIFs comprise SBUs of metals or metal ions linked together by forming covalent bonds with linking clusters on organic linking moieties, COFs are comprised of SBUs of organic linking moieties that are linked together by forming covalent bonds via linking

clusters. "Frameworks" are highly ordered and extended structures that are not based upon a centrally coordinated ion, but involve many repeated secondary building units (SBUs) linked

together. Accordingly, "frameworks" are orders of magnitude much larger than coordination complexes and have different structural and chemical properties due to the framework's open and ordered structure .

[0046] The term "functional group" or "FG" refers to specific groups of atoms within molecules that are responsible for the characteristic chemical reactions of those molecules. While the same functional group will undergo the same or similar chemical

reaction (s) regardless of the size of the molecule it is a part of, its relative reactivity can be modified by nearby functional groups. The atoms of functional groups are linked to each other and to the rest of the molecule by covalent bonds. Examples of FG that can be used in this disclosure, include, but are not limited to,

substituted or unsubstituted alkyls, substituted or unsubstituted alkenyls, substituted or unsubstituted alkynyls, substituted or unsubstituted aryls, substituted or unsubstituted hetero-alkyls, substituted or unsubstituted hetero-alkenyls, substituted or unsubstituted hetero-alkynyls, substituted or unsubstituted cycloalkyls, substituted or unsubstituted cycloalkenyls , substituted or unsubstituted hetero-aryls , substituted or unsubstituted heterocycles , halos, hydroxyls, anhydrides, carbonyls, carboxyls, carbonates, carboxylates, aldehydes, haloformyls, esters,

hydroperoxy, peroxy, ethers, orthoesters, carboxamides , amines, imines, imides, azides, azos, cyanates, isocyanates, nitrates, nitriles, isonitriles, nitrosos, nitros, nitrosooxy, pyridyls, sulfhydryls, sulfides, disulfides, sulfinyls, sulfos, thiocyanates, isothiocyanates , carbonothioyls, phosphinos, phosphonos, phosphates, Si (OH) 3, Ge(OH)₃, Sn(OH)₃, Si(SH)₄, Ge(SH)₄, As0₃H, As0₄H, P(SH)₃, As(SH)₃, S0₃H, Si (OH) ₃, Ge(OH)₃, Sn (OH) ₃, Si(SH)₄, Ge(SH)₄, Sn(SH)₄, As0₃H, As0₄H, P(SH)₃, and As(SH)₃.

[0047] The term "heterocycle" , as used in this disclosure, refers to ring structures that contain at least 1 non-carbon ring atom. A "heterocycle" for the purposes of this disclosure encompass from 1 to 12 heterocycle rings wherein when the heterocycle is greater than 1 ring the heterocycle rings are joined so that they are linked, fused, or a combination thereof. A heterocycle may be a hetero-aryl or nonaromatic, or in the case of more than one

heterocycle ring, one or more rings may be nonaromatic, one or more rings may be hetero-aryls , or a combination thereof. A heterocycle may be substituted or unsubstituted, or in the case of more than one heterocycle ring one or more rings may be unsubstituted, one or more rings may be substituted, or a combination thereof. Typically, the non-carbon ring atom is N, 0, S, Si, Al, B, or P. In case where there is more than one non-carbon ring atom, these non-carbon ring atoms can either be the same element, or combination of different elements, such as N and 0. Examples of heterocycles include, but are not limited to: a monocyclic heterocycle such as, aziridine, oxirane, thiirane, azetidine, oxetane, thietane, pyrrolidine, pyrroline, imidazolidine , pyrazolidine , pyrazoline, dioxolane, sulfolane 2, 3-dihydrofuran, 2 , 5-dihydrofuran tetrahydrofuran, thiophane, piperidine, 1 , 2 , 3 , 6-tetrahydro-pyridine , piperazine, morpholine, thiomorpholine , pyran, thiopyran, 2 , 3-dihydropyran, tetrahydropyran, 1, 4-dihydropyridine, 1,4-dioxane, 1,3-dioxane, dioxane, homopiperidine, 2, 3, 4, 7-tetrahydro-lH-azepine

homopiperazine , 1 , 3-dioxepane , 4 , 7-dihydro-l , 3-dioxepin, and hexamethylene oxide; and polycyclic heterocycles such as, indole, indoline, isoindoline, quinoline, tetrahydroquinoline , isoquinoline , tetrahydroisoquinoline , 1 , 4-benzodioxan, coumarin, dihydrocoumarin, benzofuran, 2 , 3-dihydrobenzofuran, isobenzofuran, chromene, chroman, isochroman, xanthene, phenoxathiin, thianthrene, indolizine, isoindole, indazole, purine, phthalazine, naphthyridine ,

quinoxaline, quinazoline, cinnoline, pteridine, phenanthridine , perimidine, phenanthroline , phenazine, phenothiazine, phenoxazine, 1, 2-benzisoxazole, benzothiophene, benzoxazole, benzthiazole, benzimidazole , benztriazole, thioxanthine , carbazole, carboline, acridine, pyrolizidine, and quinolizidine . In addition to the polycyclic heterocycles described above, heterocycle includes polycyclic heterocycles wherein the ring fusion between two or more rings includes more than one bond common to both rings and more than two atoms common to both rings. Examples of such bridged

heterocycles include quinuclidine, diazabicyclo [ 2.2.1 ] heptane and 7- oxabicyclo [2.2.1] heptane .

[0048] The terms "heterocyclic group", "heterocyclic moiety",

"heterocyclic", or "heterocyclo" used alone or as a suffix or prefix, refers to a heterocycle that has had one or more hydrogens removed therefrom.

[0049] The term "hetero-aryl" used alone or as a suffix or prefix, refers to a heterocycle or heterocyclyl having aromatic character. Examples of heteroaryls include, but are not limited to, pyridine, pyrazine, pyrimidine, pyridazine, thiophene, furan, furazan, pyrrole, imidazole, thiazole, oxazole, pyrazole,

isothiazole, isoxazole, 1, 2, 3-triazole, tetrazole, 1,2,3- thiadiazole, 1, 2, 3-oxadiazole, 1, 2, 4-triazole, 1, 2, 4-thiadiazole, 1, 2, 4-oxadiazole, 1, 3, 4-triazole, 1, 3, 4-thiadiazole, and 1,3,4- oxadiazole .

[0050] The term "hetero-" when used as a prefix, such as, hetero-alkyl , hetero-alkenyl , hetero-alkynyl , or hetero-hydrocarbon, for the purpose of this disclosure refers to the specified

hydrocarbon having one or more carbon atoms replaced by non-carbon atoms as part of the parent chain. Examples of such non-carbon atoms include, but are not limited to, N, 0, S, Si, Al, B, and P. If there is more than one non-carbon atom in the hetero-based parent chain then this atom may be the same element or may be a combination of different elements, such as N and 0.

[0051] The term "hydrocarbons" refers to groups of atoms that contain only carbon and hydrogen. Examples of hydrocarbons that can be used in this disclosure include, but are not limited to, alkanes, alkenes, alkynes, arenes, and benzyls.

[0052] A "linking moiety" refers to a parent chain that binds a metal or metal ion or a plurality of metals or metal ions. A linking moiety may be further substituted post synthesis by reacting with one or more post-framework reactants .

[0053] The term "linking cluster" refers to one or more atoms capable of forming an association, e.g. covalent bond, polar covalent bond, ionic bond, and Van Der Waal interactions, with one or more atoms of another linking moiety, and/or one or more metal or metal ions. A linking cluster can be part of the parent chain itself and/or additionally can arise from functionalizing the parent chain, e.g. adding carboxylic acid groups to the parent chain. For example, a linking cluster can comprise NN(H)N, N(H)NN, C0₂H, CS₂H, N0₂, SO3H, Si (OH) 3, Ge(OH)₃, Sn(OH)₃, Si(SH)₄, Ge(SH)₄, Sn(SH)₄, P0₃H, As0₃H, As0₄H, P(SH)₃, As (SH) ₃, CH(RSH)₂, C (RSH) 3, CH(RNH₂)₂, C(RNH₂)₃, CH(ROH)₂, C(ROH)₃, CH(RCN)₂, C (RCN) 3, CH(SH)₂, C(SH)₃, CH(NH₂)₂, C(NH₂)₃, CH(OH)₂, C(OH)₃, CH(CN)₂, and C(CN)₃, wherein R is an alkyl group having from 1 to 5 carbon atoms, or an aryl group comprising 1 to 2 phenyl rings and CH(SH)₂, C(SH)₃, CH(NH₂)₂, C(NH₂)₃, CH(OH)₂, C(OH)₃, CH(CN)₂, and C(CN)₃. Generally, the linking clusters disclosed herein are Lewis bases, and therefore have lone pair electrons available and/or can be deprotonated to form stronger Lewis bases. The deprotonated version of the linking clusters, therefore, are encompassed by the disclosure and anywhere a linking cluster that is depicted in a non-de-protonated form, the deprotonated form should be presumed to be included, unless stated otherwise .

[0054] A "metal" refers to a solid material that is typically hard, shiny, malleable, fusible, and ductile, with good electrical and thermal conductivity. "Metals" used herein refer to metals selected from alkali metals, alkaline earth metals, lanthanides, actinides, transition metals, and post transition metals.

[0055] A "metal ion" refers to an ion of a metal. Metal ions are generally Lewis Acids and can form coordination complexes.

Typically, the metal ions used for forming a coordination complex in a framework are ions of transition metals.

[0056] The term "mixed ring system" refers to optionally substituted ring structures that contain at least two rings, and wherein the rings are joined together by linking, fusing, or a combination thereof. A mixed ring system comprises a combination of different ring types, including cycloalkyl, cycloalkenyl , aryl, and heterocycle .

[0057] "Natural gas" refers to a multi-component gas obtained from a crude oil well (associated gas) or from a subterranean gas- bearing formation (non-associated gas) . The composition and pressure of natural gas can vary significantly. A typical natural gas stream contains methane as a significant component. The natural gas will also typically contain ethane, higher molecular weight hydrocarbons, one or more acid gases (such as carbon dioxide, hydrogen sulfide, carbonyl sulfide, carbon disulfide, and mercaptans) , and minor amounts of contaminants such as water, nitrogen, iron sulfide, wax, and crude oil.

[0058] The term "post-framework reactants" refers to all known substances that are directly involved in a chemical reaction. Post- framework reactants typically are substances, either elemental or MOF frameworks, which have not reached the optimum number of electrons in their outer valence levels, and/or have not reached the most favorable energetic state due to ring strain, bond length, low bond dissociation energy, and the like. Some examples of post- framework reactants include, but are not limited to:

wherein each R is independently selected from the group comprising: H, sulfonates, tosylates, azides, triflates, ylides, alkyl, aryl, OH, alkoxy, alkenes, alkynes, phenyl and substitutions of the foregoing, sulfur-containing groups (e.g., thioalkoxy, thionyl chloride) , silicon-containing groups, nitrogen-containing groups (e.g., amides and amines), oxygen-containing groups (e.g., ketones, carbonates, aldehydes, esters, ethers, and anhydrides) , halogen, nitro, nitrile, nitrate, nitroso, amino, cyano, ureas, boron- containing groups (e.g., sodium borohydride, and catecholborane) , phosphorus-containing groups (e.g., phosphorous tribromide) , and aluminum-containing groups (e.g., lithium aluminum hydride).

[0059] The term "substituted" with respect to hydrocarbons, heterocycles , and the like, refers to structures wherein the parent chain contains one or more substituents .

[0060] The term "substituent" refers to an atom or group of atoms substituted in place of a hydrogen atom. For purposes of this disclosure, a substituent would include deuterium atoms.

[0061] The term "unsubstituted" with respect to hydrocarbons, heterocycles, and the like, refers to structures wherein the parent chain contains no substituents .

[0062] A "BTB-based linking ligand" as used herein refers to an organic structure that comprises a 1, 3, 5-tris (4- carboxyphenyl ) enzene (BTB) core structure which may be further substituted with one or more substituents , including ring structures arising from adjacent positions on the BTB-aryl rings. While the various BTB-based linking ligands depicted herein (e.g., Formula I) are shown with carboxylic acid based linking clusters, it would be understood by one of skill in the art that these carboxylic acid groups undergo condensation to form one or more bonds to a metal or metal ion of the SBUs in order to link the SBUs together in the framework. For example, the carboxylic acid groups could be understood as having the generalized structure of:

when condensed with one or more metal ions to make a MOF of the disclosure .

[0063] Metal-organic frameworks (MOFs) composed of polymetallic inorganic clusters and polytopic organic linkers are crystalline porous materials that can be tailored by modifying the metal, linking ligand and substituents thereof, such that the interior can be systematically modified for rationally optimizing their

performance in gas separation, gas storage, and other applications. The diversity and heterogeneity of MOFs can be greatly expanded by introducing different functional groups and varying the ratios of multiple functionalities in one crystal, which has offered an exclusive opportunity to make materials with desired complexity or sequence. MOFs with hetero ( 6 , 3 ) -coordinated qom net (see FIG . 1 ) are generated from isoreticular functionalization, topological isomerization, and multivariate heterogeneity of octahedral inorganic SBU' s (e.g., Zn40(COO^")6) linked together with BTB-based linking ligands.

[0064] In synthesizing the MOFs of the disclosure, several challenges had to be overcome including, but not limited to, (1) linkers have to be generated with various functional groups; (2) the structural fidelity of the inorganic SBUs have to be maintained in- situ when using linkers with different functional groups; (3) the topology of the network resulting from linking octahedral inorganic SBU with tritopic linkers has to be resolved; and (4) the activation procedure has to be optimized in order to produce activated MOFs with high porosity.

[0065] Provided herein is a versatile synthetic route to

efficiently prepare BTB derivatives with various functional groups. As shown in FIG. 2, nine examples of BTB derivatives (from B to J) comprising different types and/or number of functional groups were utilized to synthesize the MOFs of the disclosure. For example, in one embodiment, a hetero-functionalized BTB derivative (K) , possessing three different functional groups on one linker was realized through multiple steps of coupling reactions. The

disclosure also provides nine MOFs comprising BTB-based linking moieties with various organic groups (e.g., amino, fluoro, methyl, methoxy, benzyloxy, and fused benzene) that were successfully isolated as single crystals, and which were further characterized by single-crystal diffraction (SCXRD) , powder X-ray diffraction (PXRD) , thermogravimetric analysis (TGA) , and sorption measurements. Several topological isomers of the MOFs disclosed herein were encountered in the screening reactions, by SCXRD and PXRD. A series of multivariate

(MTV) MOFs comprising different numbers and varieties of BTB-based linking ligands, including varying the ratios between the linking ligands, were also characterized by SCXRD, PXRD, TGA and sorption measurements .

[0066] The disclosure provides for MOFs that comprise a plurality of SBUs linked together by a plurality of functionalized 1 , 3 , 5-tris (4-carboxyphenyl ) benzene (BTB) -based linking ligands. The disclosure also provides for a MOF of the disclosure being

multivariate by comprising two or more BTB-based linking ligands having different structures. As demonstrated herein, the material properties of these multivariate MOFs can be modified by changing the ratio between multiple types of differently functionalized BTB- based linking ligands. In yet another embodiment, the disclosure provides for MOFs of the disclosure which comprise SBUs that are linked by two or more types of differently functionalized BTB-based linking ligands, wherein the different types of functional groups on the BTB-based linking ligands modify the chemical and physical properties of a MOF of the disclosure. The structural tunability of the MOFs disclosed herein exceeds that of previously known systems, allowing for an extremely high level of optimization for various applications such as gas separation, gas storage, water storage and release, or catalysis.

[0067] It should be understood that for MOFs disclosed herein that comprise multiple types of differently functionalized organic linking ligands, that such linking ligands can originate from (1) organic linking ligands that are differentially functionalized presynthesis (i.e., constructing the framework with organic linking ligands that differ by the number and/or type of functional groups) ;

(2) organic linking ligands that comprise functional groups that are modified post-synthesis of the framework by reacting the functional group with a post-framework reactant; (3) organic linking ligands comprising functional group (s) that are protected with a suitable protecting group which can then be removed post-synthesis of the framework, wherein the de-protected functional groups may be modified by reacting with a post-framework reactant; and (4) organic linking ligands that comprise functional groups which are protected with one type of protecting group while other functional groups are protected with a different type of protecting group, such that the protecting groups can be differentially removed post-synthesis of the framework by using different reaction conditions; using such a strategy, one can selectively de-protect certain functional groups while leaving other functional groups protected, so that the newly de-protected groups may be modified by reacting with a post- framework reactant, the remaining protected functional groups may then be de-protected and be modified if so desired by reacting with a post-framework reactant, etc.

[0068] In a certain embodiment, a MOF of the disclosure comprises a plurality of SBUs which comprise metal or metal ions selected from: Li⁺, Na⁺, K⁺, Rb⁺, Cs⁺, Be²⁺, Ca²⁺, Sr²⁺, Ba²⁺, Sc³⁺, Sc²⁺, Sc⁺, Y³⁺, Y²⁺, Y\ Ti⁴⁺, Ti³⁺, Ti²⁺, Zr⁴⁺, Zr³⁺, Zr²⁺, Hf⁴⁺, Hf³⁺, V⁵⁺, V⁴⁺, V³⁺, V²⁺, Nb⁵⁺, Nb⁴⁺, Nb³⁺, Nb²⁺, Ta⁵⁺, Ta⁴⁺, Ta³⁺, Ta²⁺, Cr⁶⁺, Cr⁵⁺, Cr⁴⁺, Cr³⁺, Cr²⁺, Cr⁺, Cr, Mo⁶⁺, Mo⁵⁺, Mo⁴⁺, Mo³⁺, Mo²⁺, Mo⁺, Mo, W⁶⁺, W⁵⁺, W⁴⁺, W³⁺, W²⁺, W⁺, W, Mn⁷⁺, Mn⁶⁺, Mn⁵⁺, Mn⁴⁺, Mn³⁺, Mn²⁺, Mn⁺, Re⁷⁺, Re⁶⁺, Re⁵⁺, Re⁴⁺, Re³⁺, Re²⁺, Re⁺, Re, Fe⁶⁺, Fe⁴⁺, Fe³⁺, Fe²⁺, Fe⁺, Fe, Ru⁸⁺, Ru⁷⁺, Ru⁶⁺, Ru⁴⁺, Ru³⁺, Ru²⁺, Os⁸⁺, Os⁷⁺, Os⁶⁺, Os⁵⁺, Os⁴⁺, Os³⁺, Os²⁺, Os⁺, Os, Co⁵⁺, Co⁴⁺, Co³⁺, Co²⁺, Co⁺, Rh⁶⁺, Rh⁵⁺, Rh⁴⁺, Rh³⁺, Rh²⁺, Rh⁺, Ir⁶⁺, Ir⁵⁺,

Ir⁴⁺, Ir³⁺, Ir²⁺, Ir⁺, Ir, Ni³⁺, Ni²⁺, Ni⁺, Ni, Pd⁶⁺, Pd⁴⁺, Pd²⁺, Pd⁺, Pd,

Pt⁶⁺, Pt⁵⁺, Pt⁴⁺, Pt³⁺, Pt²⁺, Pt⁺, Cu⁴⁺, Cu³⁺, Cu²⁺, Cu⁺, Ag³⁺, Ag²⁺, Ag⁺,

Au⁵⁺, Au⁴⁺, Au³⁺, Au²⁺, Au⁺, Zn²⁺, Zn⁺, Zn, Cd²⁺, Cd⁺, Hg⁴⁺, Hg²⁺, Hg⁺, B³⁺,

B²⁺, ] 3⁺, Al ³⁺, Al ²⁺, Al ⁺, Ga ³⁺, Ga²⁺, Ga⁺, In³⁺, In²⁺, In¹⁺, Tl³⁺, Tl⁺, Si⁴⁺,

Si³⁺, Si²⁺, Si⁺, Ge⁴⁺, Ge³⁺, Ge²⁺, Ge⁺, Ge, Sn⁴⁺, Sn²⁺, Pb⁴⁺, Pb²⁺, As⁵⁺,

As³⁺, As²⁺, As⁺, Sb⁵⁺, Sb³⁺, Bi⁵⁺, Bi³⁺, Te⁶⁺, Te⁵⁺, Te⁴⁺, Te²⁺, La³⁺, La²⁺,

Ce⁴⁺, Ce³⁺, Ce²⁺, Pr⁴⁺, Pr³⁺, Pr²⁺, Nd³⁺, Nd²⁺, Sm³⁺, Sm²⁺, Eu³⁺, Eu²⁺, Gd³⁺,

Gd²⁺, Gd⁺, Tb⁴⁺, Tb³⁺, Tb²⁺, Tb⁺, Db³⁺, Db²⁺, Ho³⁺, Er³⁺, Tm⁴⁺, Tm³⁺, Tm²⁺,

Yb³⁺, Yb²⁺, Lu³⁺, La³⁺, La²⁺, La⁺, including any complexes which contain the metals or metal ions, as well as any corresponding metal salt counter-anions .

[0069] In a further embodiment, a MOF of the disclosure

comprises a plurality of SBUs comprising zinc metal ions, including complexes which contain the zinc metal ions, as well as any

corresponding metal salt counter-anions.

[0070] In a particular embodiment, the disclosure provides for

MOFs that comprise a plurality of SBUs that are linked together by a plurality of BTB-based linking ligands that comprise a structure of Formula I :

Formula (I)

wherein,

A¹-A³ are independently a C-H or N;

optionally substituted (C1-C12) cycloalkyl, optionally substituted

(C1-C12) cycloalkenyl, optionally substituted aryl, optionally substituted heterocycle, optionally substituted mixed ring system, - C(R¹³)₃, -CH(R¹³)₂, -CH2R¹³, -C(R¹⁴)₃, -CH(R¹⁴)₂, -CH₂R¹⁴, -OC(R¹³)₃, OCH(R¹³)₂, -OCH2R¹³, -OC(R¹⁴)₃, -OCH(R¹⁴)₂, OCH₂R¹⁴, wherein R^x-R¹² when adjacent can be linked together to form one or more optionally substituted rings selected from the group comprising cycloalkyl, cycloalkenyl, heterocycle, aryl, and mixed ring system;

R¹³ is selected from FG, optionally substituted (C1-C12) alkyl, optionally substituted hetero- (C1-C12) alkyl, optionally substituted

(C1-C12) alkenyl, optionally substituted hetero- (C1-C12) alkenyl, optionally substituted (C1-C12) alkynyl, optionally substituted hetero- (Ci- C12) alkynyl, hemiacetal, hemiketal, acetal, ketal, and orthoester; and

R¹⁴ is selected from one or more substituted or unsubstituted rings selected from cycloalkyl, aryl and heterocycle. In a particular embodiment, at least one of R^x-R¹² is not an H. In another embodiment, the MOF comprises at least two, three, four, five or six structurally different linking ligands of Formula I

(e.g., the linking ligands comprise different R-groups) .

[ 0071 ] In another embodiment, the disclosure provides for a MOF that comprises a plurality SBUs that are linked together by a plurality of BTB-based linking ligands that comprise a structure of Formula I :

30

wherein M is an alkaline metal species, an alkaline-earth metal species, or transition metal species that has a formal charge of +1 and that can be coordinated by one or more neutral or charged ligands; and wherein at least one of R^x-R¹² is not H when A¹-A³ are C.

[ 0072 ] In an alternate embodiment, the disclosure provides for a

MOF that is multivariate by being comprised of a plurality SBUs that are linked together by a plurality of differently functionalized BTB-based linking ligands that comprise a structure of Formula I :

wherein M is an alkaline metal species, an alkaline-earth metal species, or transition metal species that has a formal charge of +1 and that can be coordinated by one or more neutral or charged ligands .

[ 0073 ] In a further embodiment, a MOF of disclosure comprises a

BTB-based linking ligand selected from:

and CH, CH, OH

[0074] In another embodiment, a MOF of the disclosure is multivariate and comprises at least two BTB-based linking ligands selected from:

[0075] It is yet further contemplated by this disclosure that to enhance chemo-selectivity it may be desirable to protect one or more functional groups that would generate unfavorable products upon a chemical reaction desired for another functional group, and then deprotect this protected group after the desired reaction is completed. Employing such a protection/deprotection strategy could be used for one or more functional groups of any organic linking ligand described herein, including any structures depicted herein. Accordingly, hydroxyl groups may further comprise a hydroxyl protecting group, amine groups may further comprise an amine protecting group, and carbonyl groups may further comprise a carbonyl protecting group, unless stated otherwise herein.

[0076] Examples of hydroxyl protecting groups include, but are not limited to, methyl, tert-butyl, allyl, propargyl, p- chlorophenyl , p-methoxyphenyl , p-nitrophenyl , 2, 4-dinitrophenyl, 2,3,5, 6-tetrafluoro-4- (trifluoromethyl) phenyl, methoxymethyl , methylthiomethyl , (phenyldimethylsilyl ) methoxymethyl , benzyloxymethyl , p-methoxy-benzyloxymethyl , p-nitrobenzyloxymethyl, o-nitrobenzyloxymethyl , (4-methoxyphenoxy) methyl, guaiacolmethyl , tert-butoxymethyl , 4-pentenyloxymethyl, tert- butyldimethylsiloxymethyl , thexyldimethylsiloxymethyl , tert- butyldiphenylsiloxymethyl , 2-methoxyethoxymethyl, 2,2,2- trichloroethoxymethyl , bis (2-chloroethoxy) methyl, 2-

(trimethylsilyl) ethoxymethyl, menthoxymethyl , 1-ethoxyethyl, 1- (2- chloroethoxy) ethyl, 1- [2- (trimethylsilyl) ethoxy] ethyl, 1-methyl-l- ethoxyethyl, 1-methyl-l-benzyloxyethyl, l-methyl-l-benzyloxy-2- fluoroethyl, 1-methyl-l-phenoxyethyl, 2 , 2 , 2-trichloroethyl , 1- dianisyl-2 , 2 , 2-trichloroethyl, 1,1,1,3,3, 3-hexafluoro-2- phenylisopropyl , 2-trimethylsilylethyl, 2- (benzylthio) ethyl, 2-

(phenylselenyl ) ethyl, tetrahydropyranyl , 3-bromotetrahydropyranyl , tetrahydrothiopyranyl , 1-methoxycyclohexyl, 4- methoxytetrahydropyranyl , 4-methoxytetrahydrothiopyranyl , 4- methoxytetrahydropyranyl S, S-dioxide, 1- [ (2-chloro-4-methyl) phenyl] - 4-methoxypiperidin-4-yl, 1- (2-fluorophenyl) -4-methoxypiperidin-4-yl, 1, 4-dioxan-2-yl, tetrahydrofuranyl , tetrahydrothiofuranyl and the like; Benzyl, 2-nitrobenzyl, 2-trifluoromethylbenzyl, 4- methoxybenzyl , 4-nitrobenzyl, 4-chlorobenzyl, 4-bromobenzyl, 4- cyanobenzyl, 4-phenylbenzyl, 4-acylaminobenzyl, 4-azidobenzyl, 4-

(methylsulfinyl) benzyl, 2, 4-dimethoxybenzyl, 4-azido-3-chlorobenzyl, 3, 4-dimethoxybenzyl, 2 , 6-dichlorobenzyl , 2, 6-difluorobenzyl, 1- pyrenylmethyl , diphenylmethyl , 4 , 4 ' -dinitrobenzhydryl , 5- benzosuberyl , triphenylmethyl (trityl), . alpha. - naphthyldiphenylmethyl , (4-methoxyphenyl) -diphenyl-methyl , di- (p- methoxyphenyl ) -phenylmethyl, tri- (p-methoxyphenyl ) methyl, 4- (4 ' - bromophenacyloxy) -phenyldiphenylmethyl , 4, 4 ' , 4 ' ' -tris (4,5- dichlorophthalimidophenyl ) methyl, 4, 4 ' , 4 ' ' - tris ( levulinoyloxyphenyl ) methyl, 4,4' -dimethoxy-3 ' ' - [N- ( imidazolylmethyl ) ] trityl, 4,4' -dimethoxy-3 ' ' - [N- ( imidazolylethyl ) carbamoyl] trityl, 1, 1-bis (4-methoxyphenyl) -1 ' - pyrenylmethyl , 4-(l 7-tetrabenzo [a, c, g, I ] fluorenylmethyl) -4, 4 '- dimethoxytrityl , 9-anthryl, 9- ( 9-phenyl ) xanthenyl , 9- ( 9-phenyl-10- oxo)anthryl and the like; Trimethylsilyl, triethylsilyl ,

triisopropylsilyl , dimethylisopropylsilyl , diethylisopropylsilyl, dimethylhexylsilyl , tert-butyldimethylsilyl, tert- butyldiphenylsilyl , tribenzylsilyl , tri-p-xylylsilyl ,

triphenylsilyl , diphenylmethylsilyl, di-tert-butylmethylsilyl , tris (trimethylsilyl) silyl, (2-hydroxystyryl) dimethylsilyl , (2- hydroxystyryl ) diisopropylsilyl , tert-butylmethoxyphenylsilyl , tert- butoxydiphenylsilyl and the like; --C(0)R⁴⁰, where R⁴⁰ is selected from the group consisting of alkyl, substituted alkyl, aryl and more specifically R⁴⁰ = hydrogen, methyl, ethyl, tert-butyl, adamantyl, crotyl, chloromethyl , dichloromethyl , trichloromethyl ,

trifluoromethyl, methoxymethyl , triphenylmethoxymethyl ,

phenoxymethyl , 4-chlorophenoxymethyl, phenylmethyl , diphenylmethyl, 4-methoxycrotyl, 3-phenylpropyl , 4-pentenyl, 4-oxopentyl, 4,4- (ethylenedithio) pentyl, 5- [3-bis (4- methoxyphenyl) hydroxymethylphenoxy] -4-oxopentyl, phenyl, 4- methylphenyl , 4-nitrophenyl, 4-fluorophenyl, 4-chlorophenyl, 4- methoxyphenyl , 4-phenylphenyl, 2 , 4 , 6-trimethylphenyl , a-naphthyl, benzoyl and the like; --C(0)OR⁴¹, where R⁴¹ is selected from the group consisting of alkyl, substituted alkyl, aryl and more specifically R⁴¹ = methyl, methoxymethyl, 9-fluorenylmethyl , ethyl, 2, 2, 2-trichloromethyl, 1 , l-dimethyl-2 , 2 , 2-trichloroethyl , 2- (trimethylsilyl) ethyl, 2- (phenylsulfonyl) ethyl, isobutyl, tert- butyl, vinyl, allyl, 4-nitrophenyl, benzyl, 2-nitrobenzyl, 4- nitrobenzyl, 4-methoxybenzyl, 2, 4-dimethoxybenzyl, 3,4- dimethoxybenzyl , 2- (methylthiomethoxy) ethyl, 2-dansenylethyl, 2- (4- nitrophenyl) ethyl, 2- (2, 4-dinitrophenyl) ethyl, 2-cyano-l- phenylethyl, thiobenzyl, 4-ethoxy-l-naphthyl and the like.

[ 0077 ] Examples of carbonyl protecting groups include, but are not limited to, dimethyl acetal, 1-3-dioxane, 1-3-dioxolane, S, S'- dimethylthioacetal , 1 , 3-dithiane , 1 , 3-dithiolane , 1 , 3-oxathiolane , methyl ester, t-Butyl ester, allyl ester, 1, 1-dimethylallyl ester, 2 , 2 , 2-trifluoroethyl ester, phenyl ester, benzyl ester, 4- methoxybenzyl ester, silyl ester, ortho ester, 9-fluorenylmethyl esters, 2- (trimethylsilyl) ethoxymethyl ester, 2- (trimethylsily) ethyl ester, halo esters, o-nitrobenzyl ester, and OBO ester.

[ 0078 ] Examples of amine protecting groups include, but are not limited to, methyl carbonate, 9-fluorenylmethyl carbamate (Fmoc) , 2 , 2 , 2-trichloroethyl carbamate (Troc) , t-butyl carbamate (Boc) , 2- (trimethylsilyl) ethyl carbamate (Teoc) , allyl carbamate (Alloc), benzyl carbamate (Cbz), trifluoroacetamide , benzylamine, allylamine, and tritylamine .

[ 0079 ] All the aforementioned linking ligands that possess appropriate reactive functionalities can be chemically transformed by a suitable reactant post synthesis of the framework to add further functionalities to the framework. By modifying the organic links within the framework post-synthetically, access to functional groups that were previously inaccessible or accessible only through great difficulty and/or cost is possible and facile.

[ 0080 ] The MOFs of the disclosure may be generated by first utilizing a plurality of BTB-based linking ligands having different functional groups, wherein at least one of the functional groups may be modified, substituted, or eliminated with a different functional group post-synthesis of the framework. In other words, at least one BTB-based linking ligand comprises a functional group that may be reacted with a post-framework reactant to further increase the diversity of the functional groups of the MOFs disclosed herein. In a particular embodiment, the MOF disclosed herein comprises multiple types of differently functionalized BTB-based linking ligands wherein one or more types of the linking ligands can undergo postsynthetic modification with post-framework reactant so as to further functionalize the framework.

[ 0081 ] In a further embodiment, the MOFs of the disclosure may be further modified by reacting with one or more post-framework reactants that may or may not have denticity. In another embodiment, a MOF as-synthesized is reacted with at least one, at least two, or at least three post-framework reactants. In yet another embodiment, a MOF as-synthesized is reacted with at least two post-framework reactants. In a further embodiment, a MOF as-synthesized is reacted with at least one post-framework reactant that will result in adding denticity to the framework.

[ 0082 ] The disclosure provides that a MOF disclosed herein can be modified by a post-framework reactant by using chemical reactions that modify, substitute, or eliminate a functional group post- synthesis. These chemical reactions may use one or more similar or divergent chemical reaction mechanisms depending on the type of functional group and/or post-framework reactant used in the reaction. Examples of chemical reaction include, but are not limited to, radical-based, unimolecular nuclephilic substitution (SN1) , bimolecular nucleophilic substitution (SN2), unimolecular elimination (El), bimolecular elimination (E2), ElcB elimination, nucleophilic aromatic substitution (SnAr) , nucleophilic internal substitution (SNi) , nucleophilic addition, electrophilic addition, oxidation, reduction, cycloadition, ring closing metathesis (RCM) , pericylic, electrocylic, rearrangement, carbene, carbenoid, cross coupling, and degradation. Other agents can be added to increase the rate of the reactions disclosed herein, including adding catalysts, bases, and acids.

[0083] In another embodiment, a post-framework reactant adds at least one effect to a MOF of the disclosure including, but not limited to, modulating the gas storage ability of the MOF;

modulating the sorption properties of the MOF; modulating the pore size of the MOF; modulating the catalytic activity of the MOF;

modulating the conductivity of the MOF; modifying the heat or chemical stability of the MOF; and modulating the sensitivity of the MOF to the presence of an analyte of interest. In a further embodiment, a post-framework reactant adds at least two effects to the MOF of the disclosure including, but not limited to, modulating the gas storage ability of the MOF; modulating the sorption properties of the MOF; modulating the pore size of the MOF;

modulating the catalytic activity of the MOF; modulating the conductivity of the MOF; and modulating the sensitivity of the MOF to the presence of an analyte of interest.

[0084] In one embodiment, a post-framework reactant can be a saturated or unsaturated heterocycle.

[0085] In another embodiment, a post-framework reactant has 1-20 carbons with functional groups including atoms such as N, S, and 0.

[0086] In yet another embodiment, a post-framework reactant is selected to modulate the size of the pores of a MOF disclosed herein .

[0087] In another embodiment, a post-framework reactant is selected to increase the hydrophobicity of a MOF disclosed herein. [ 0088 ] In yet another embodiment, a post-framework reactant is selected to modulate gas separation of a MOF disclosed herein. In a certain embodiment, a post-framework reactant creates an electric dipole moment on the surface of a MOF of the disclosure when it chelates a metal ion.

[ 0089 ] In a further embodiment, a post-framework reactant is selected to modulate the gas sorption properties of a MOF of the disclosure. In another embodiment, a post-framework reactant is selected to promote or increase greenhouse gas sorption of a MOF disclosed herein. In another embodiment, a post-framework reactant is selected to promote or increase hydrocarbon gas sorption of a MOF of the disclosure.

[ 0090 ] In yet a further embodiment, a post-framework reactant is selected to increase or add catalytic efficiency to a MOF disclosed herein .

[ 0091 ] In another embodiment, a post-framework reactant is selected so that organometallic complexes can be tethered to a MOF of the disclosure. Such tethered organometallic complexes can be used, for example, as heterogeneous catalysts.

[ 0092 ] In a particular embodiment, a MOF of the disclosure can be used for a variety of applications, including for gas, liquid or vapor separation, gas storage, separation of bioproducts or compounds, or catalysis. In particular embodiment, the disclosure provides for MOFs that can be tuned to adsorb a specific gas or multiple gases from mixed gas stream. For example, a MOF disclosed herein that is comprised of multiple types of BTB-based linking ligands can provide functional groups that have differential binding/interaction characteristics for specific gas molecules.

Further, in comparison to other BTB-based frameworks, such as MOF- 177, the MOFs of the disclosure have enhanced adsorption affinities and stabilities for fuel energy gases, such as hydrogen and methane, which allows for use of the MOFs in high density storage

applications at lower pressures, such as in Absorbed Natural Gas

(ANG) tanks for vehicles and other equipment.

[ 0093 ] In one embodiment of the disclosure, a gas storage or gas separation material comprising a MOF of the disclosure is provided. Advantageously, a MOF of the disclosure includes a number of adsorption sites for storing and/or separating gas molecules.

Suitable examples of such gases include, but are not limited to, gases comprising ammonia, argon, methane, propane, carbon dioxide, carbon monoxide, sulfur dioxide, hydrogen sulfide, phosphine, nitrous oxide, hydrogen, oxygen, nitrogen, fluorine, chlorine, helium, carbonyl sulfide, and combinations thereof. In a

particularly useful variation a MOF disclosed herein is a fuel gas storage material that is used to fuel gases, such as hydrogen and methane. In another particularly useful variation, a MOF disclosed herein is a carbon dioxide storage material that may be used to separate hydrogen from a gaseous mixture. In yet another

particularly useful variation, a MOF disclosed herein is a methane storage material that may be used to separate methane from a gaseous mixture .

[0094] The disclosure also provides an apparatus and method for separating one or more components from a multi-component gas using a separation system having a feed side and an effluent side separated by a MOF of the disclosure. The apparatus may comprise a column separation format.

[0095] A MOF of the disclosure can be used as an adsorbent for methane. In a certain embodiment, a MOF disclosed herein can be used to separate and/or store one or more gases from a natural gas stream. In another embodiment, a MOF disclosed herein can be used to separate and/or store methane from a natural gas stream. In yet another embodiment, a MOF disclosed herein can be used to separate and/or store methane from a town gas stream. In yet another embodiment, a MOF disclosed herein can be used to separate and/or store methane from a biogas stream. In a certain embodiment, a MOF disclosed herein can be used to separate and/or store methane from a syngas stream.

[0096] In a particular embodiment, a MOF disclosed herein is part of a device. In another embodiment, a gas separation device comprises a MOF of the disclosure. In a further embodiment, a gas separation device used to separate one or more component gases from a multi-component gas mixture comprises a MOF disclosed herein.

Examples of gas separation and/or gas storage devices include, but are not limited to, purifiers, filters, scrubbers, pressure swing adsorption devices, molecular sieves, hollow fiber membranes, ceramic membranes, cryogenic air separation devices, and hybrid gas separation devices. In a certain embodiment, a gas separation device used to separate methane and/or hydrogen from a mixed gas stream comprises a MOF of the disclosure.

[0097] In a particular embodiment of the disclosure, a gas storage material comprises a MOF disclosed herein. A gas that may be stored or separated by the methods, compositions and systems of the disclosure includes gases selected from the group consisting of ammonia, argon, methane, propane, carbon dioxide, carbon monoxide, sulfur dioxide, hydrogen sulfide, phosphine, nitrous oxide, hydrogen, oxygen, nitrogen, fluorine, chlorine, helium, carbonyl sulfide, and combinations thereof. In a particularly useful variation a gas storage material is a hydrogen storage material that is used to store hydrogen (¾) . In another particularly useful variation, a gas storage material is a methane storage material that may be used to store methane .

[0098] In a certain embodiment, a MOF of the disclosure can be used as heterogeneous catalysts. A MOF can be synthesized to have catalytic activity or be functionalized post-synthetically with a post-framework reactant to become catalytic. Catalytic activities would include, but are not limited to, hydrolysis reactions, oxidations, reductions, ring closure reactions, metathesis

reactions, and isomerizations .

[0099] In another embodiment, a MOF of the disclosure can be used as a sensor. For example, a MOF of the disclosure can adsorb or absorb to an analyte gas of interest and which upon binding to the analyte undergo a detectable change that can be measure by a transducer thereby indicating the presence of an absorbed analyte. For example, the disclosure provides a MOF of the disclosure comprising a porous frameworks that can be used in any number of sensor modalities comprising different transducers for measuring a detectable signal. Chemically-sensitive resistor, for example, can be used wherein the sensing region comprises a porous framework of the disclosure either alone or in combination with other conductive or non-conductive materials. In this embodiment, a MOF of the disclosure that is conductive and that absorbs or adsorbs and analytes of interest separates to conductive leads. When an analyte is absorbed or adsorbed by the MOF, the conductivity across the MOF changes. Such sensors can be used in a sensing array. The change in the electrical resistance of a chemically-sensitive resistor in such a sensing array can be related to the sorption of a molecule of interest to the porous framework.

[ 00100 ] Other sensor modalities include acoustic wave,

capacitance and optical transduction methods . Acoustic wave sensors measure an absorbed material by change in the vibrational frequency of the sensor (e.g., a sensor comprising a MOF of the disclosure) . For instance, an acoustic wave sensor may have a first vibrational frequency in the absence of a bound analyte and a second different frequency in the presence of the bound analyte. Measuring such changes in vibrational frequency can be performed in the methods and compositions of the disclosure wherein the sensor comprises a MOF and wherein the MOF changes mass (thus vibrational frequency) when the material binds an analyte.

[ 00101 ] Similarly, the presence of a bound analyte can be measured optically. In optical transduction modalities the optical properties are measured in a MOF prior to contact with an analyte and then subsequent to contact with the analyte. Light diffusion through a sensor material can be detected or a change in the color of the material may be detected.

[ 00102 ] Another type of sensor includes, for example, a sensor that undergoes a volume change in response to an analyte species. As the sensors are modulated in size the sensor material changes with respect to mass or optics. For example, the light diffraction indicates the presence or absence of the analyte that causes the sensing material to change. In this embodiment, the sensor material comprises a MOF of the disclosure that can be

functionalized for binding an analyte of interest either reversibly or irreversibly.

[ 00103 ] Yet another type of sensor includes those wherein the sensors produce a spectral recognition patterns when an analyte is present. In this embodiment the porous sensor material changes in optical properties, whether by density or through a change in emission, excitation or absorbance wavelengths. [ 00104 ] Any number of sensor combinations comprising a MOF of the disclosure or any number of transduction modalities can be used. For example, each individual sensor can provide a signal (e.g., a transduced signal indicative of the presence of an analyte) or a plurality of signals from an array of sensors can be used to identify an analyte of interest in a fluid. The signal transduction mechanism through which the analyte or molecule produces a signal is potentially quite broad. These include arrays of surface acoustic wave devices, quartz crystal micro-balances, dye-coated fiber optics, resistometric, electrochemical, and others modalities readily identifiable to those skilled in the art. Accordingly, transduction mechanisms include, for example optical, electrical, and/or resonance.

[ 00105 ] By "differentially responsive sensors" is meant any number of sensors comprising a MOF of the disclosure that respond (e.g., transducer a signal) to the presence or interaction of an analyte with the sensor. Such measurable changes include changes in optical wavelengths, transparency of a sensor, resonance of a sensor, resistance, diffraction of light and/or sound, and other changes easily identified to those skilled in the art.

[ 00106] The disclosure also provides methods using a MOF disclosed herein. In a certain embodiment, a method to separate or store one or more gases comprises contacting one or more gases with a MOF of the disclosure. In a further embodiment, a method to separate or store one or more gases from a mixed gas mixture comprises contacting the gas mixture with a MOF disclosed herein. In a certain embodiment, a method to separate or store one or more gases from a fuel gas stream comprises contacting the fuel gas stream with a MOF disclosed herein. In a further embodiment, a method to separate or store methane from a natural gas stream comprises contacting the natural gas stream with a MOF disclosed herein. In a certain embodiment, a method to separate or store one or more gases from flue-gas comprises contacting the flue-gas with a MOF disclosed herein. In an alternate embodiment, a MOF disclosed herein can be used to separate compounds or bioproducts from other products or solvents. Examples of such separation include the use of the MOFs disclosed herein in size exclusion chromatography, affinity chromatography, or as molecular sieves.

[ 00107 ] Sorption is a general term that refers to a process resulting in the association of atoms or molecules with a target material. Sorption includes both adsorption and absorption.

Absorption refers to a process in which atoms or molecules move into the bulk of a porous material, such as the absorption of water by a sponge. Adsorption refers to a process in which atoms or molecules move from a bulk phase (that is, solid, liquid, or gas) onto a solid or liquid surface. The term adsorption may be used in the context of solid surfaces in contact with liquids and gases. Molecules that have been adsorbed onto solid surfaces are referred to generically as adsorbates, and the surface to which they are adsorbed as the substrate or adsorbent. Adsorption is usually described through isotherms, that is, functions which connect the amount of adsorbate on the adsorbent, with its pressure (if gas) or concentration (if liquid) . In general, desorption refers to the reverse of

adsorption, and is a process in which molecules adsorbed on a surface are transferred back into a bulk phase. In a preferred embodiment, a MOF of the disclosure is used as adsorbent for natural gas in Absorbed Natural Gas (ANG) tank.

[ 00108 ] MOFs of the disclosure can be used as standard compounds for sorption instruments, and obtained results would be helpful to improve various industrial plants (i.e. separation or recovery of chemical substance) .

[ 00109 ] In a variation of this embodiment, the gaseous storage site comprises a MOF with a pore which has been functionalized with a group having a desired size or charge. In a refinement, this activation involves removing one or more chemical ligands (guest molecules) from a MOF disclosed herein. Typically, such guest molecules include species such as water, solvent molecules contained within a MOF disclosed herein, and other chemical ligands having electron density available for attachment.

[ 00110 ] A MOFs used in the embodiments of the disclosure include a plurality of pores for gas adsorption. In one variation, the plurality of pores has a unimodal size distribution. In another variation, the plurality of pores have a multimodal (e.g., bimodal) size distribution.

[ 00111 ] The following examples are intended to illustrate but not limit the disclosure. While they are typical of those that might be used, other procedures known to those skilled in the art may alternatively be used.

EXAMPLES

[ 00112 ] Materials: Zinc nitrate hexahydrate (Zn (N0₃) 2 · 6H₂0) was purchased from Fisher Scientific; 1, 3, 5-tris (4-carboxyphenyl) benzene

(H3BTB) was purchased from TCI America; anhydrous N,N- dimethylformamide (DMF) was obtained from EMD Chemicals; anhydrous acetone (purity ≥ 99.8 %, extra dry with AcroSeal) was purchased from Acros Organics; anhydrous dichloromethane (purity ≥ 99.8 %; amylene stabilized) and chloroform (pentene stabilized, HPLC grade) were purchased from Sigma-Aldrich Co and Fisher Scientific, respectively. N, ZV-diethylformamide (DEF) was provided by BASF SE

(Ludwigshafen, Germany) which was further purified by stirring with charcoal and reduced-pressure distillation. All starting materials and solvents, except DEF, were used without further purification.

[ 00113 ] X-ray diffraction analysis: X-ray diffraction (SXRD) data were collected on a Bruker D8-Venture diffractometer equipped with Mo- = 0.71073 A) and Cu-target (λ = 1.54184 A) micro-focus X-ray tubes and a PHOTON 100 CMOS detector, unless indicated otherwise. Additional data were collected using synchrotron radiation in the beamline 11.3.1 of the Advanced Light Source, LBNL . Powder X-ray diffraction patterns were recorded using a Bruker D8 Advance diffractometer (Gobel-mirror monochromated Cu Ka radiation λ = 1.54056 A) .

[ 00114 ] Elemental Mircoanalysis (ΞΑ) analysis and Nuclear

Magnetic Resonance (NMR) : Solution ^XH NMR spectra were acquired on a Bruker AVB-400 NMR spectrometer. EA were performed using a Perkin Elmer 2400 Series II CHNS elemental analyzer, solution ^XH nuclear magnetic resonance (NMR) spectra were acquired on a Bruker AVB-400 NMR spectrometer. Attenuated total reflectance (ATR) FTIR spectra of neat samples were performed using a Bruker ALPHA Platinum ATR-FTIR Spectrometer equipped with a single reflection diamond ATR module. [ 00115 ] Thermal gravimetric analysis: TGA curves were recorded on a TA Q500 thermal analysis system at a heating rate of 5 °C/min under N₂ flow.

[ 00116 ] Isotherm analysis: Ultra-high-purity grade N2, ¾, CH4, CO2 and He gases (Praxair, 99.999% purity) were used for the adsorption measurements. To estimate the porosity and specific surface area of MOFs, N2 adsorption isotherms at 77 K were recorded on a Quantachrome Quardsorb-SI volumetric gas adsorption analyzer. To estimate the low-pressure gas uptakes and adsorption heats of MOFs, H₂ (at 77 and 87 K) , CH₄ (at 273, 283 and 298 K) and C0₂ (at 273, 283 and 298 K) adsorption isotherms were recorded on a

Quantachrome Autosorb-1 volumetric gas adsorption analyzer. Liquid nitrogen and argon baths were used for the measurements at 77 and 87 K, respectively. Other temperature measurements were made by using a water bath with a circulator. Helium was used for the estimation of dead space throughout all adsorption measurements.

[ 00117 ] Design strategy of BTB derivatives. The design of BTB derivatives can be classified depending on different functionalized positions (X^x-X⁴)

H₃BTB Derivatives

Most of BTB based linking ligands were functionalized on the X³ position with different functional groups (B, C, D, E, H, and I), while one linker was functionalized on the X² position (J) . Linker F and G were simultaneously functionalized on X³/X⁴ and X²/X³

positions, respectively. The functional groups included amino, fluoro, methyl, methoxy, benzyloxy, and fused benzene groups. The functional group effects on the topology control, heterogeneity formation, and adsorption behavior of the resulting MOFs can therefore be comprehensively studied.

[00118] Synthesis of BTB-based linking ligands : Homotopically functionalized BTB linkers can be synthesized through a versatile route by coupling the 1, 3, 5-tris (4, 4, 5, 5-tetramethyl-l, 3, 2- dioxaborolan-2-yl) benzene with methyl-4-bromobenzoate analogs bearing desired functionalities, which were further hydrolyzed and acidified to provide the acid forms of the linkers (see SCHEME 1) .

SCHEME 1. General synthetic route of homotopically functionalized BTB linkers; - = -NH₂ , -F , -Me, -OMe, -OBn, -N0₂, and etc.

[00119] Heterotopically functionalized BTB linkers can be prepared by coupling sequentially of three different (4-

(methoxycarbonyl ) -phenyl ) -boronic acids or esters onto a

tribromobenzene or 1 , 3-dibromo-5-iodobenzene (see SCHEME 2). This strategy is illustrated by the synthesis of a heterotopic BTB derivative, H₃BTBNH₂-Nap (see FIG. 2K) .

Dioxane / H20 Dioxane / H20

(v:v = 2 : 1) (v:v = 2 : 1)

SCHEME 2. Stepwise synthetic route of heterotopically functionalized BTB linkers (i.e.; = H, ' = Nap, R' ' = NH₂) .

[ 00120 ] Scheme 3 provides a further depiction of the synthesis rout for organic linkers based upon Suzuki-Miyaura cross-cpuling reactions. For example, the syntheses of the acid forms of BTB derivative organic linkers with various functional groups are based on the palladium-catalyzed Suzuki-Miyaura cross-coupling reactions to produce their ester forms with further saponification and acidification. There are two routes to synthesize the ester form of organic linkers: (1) Synthesize different (4-

(methoxycarbonyl ) phenyl ) oronic acids (or their pinacol esters) with desired functional group on them, and further coupling with 1,3,5- tribromobenzene ; and (2) Synthesize the 1 , 3, 5-tris (boronic pinacol ester) benzene, and coupling with different functionalized 4- bromobenzoate esters, which are more commercial available leading to less synthetic work. In the experiments described herein both routes wer eused depending on the convenience of getting the functionalized

(4- (methoxycarbonyl) phenyl) boronic acids (or their pinacol esters), but most of them can be synthesized adopting the synthetic route 2.

[ 00121 ] Scheme 3: Syntheses of organic linkers based on Suzuki- Miyaura cross-coupling reactions:

{54% yield) (47% yie!cl) (43% yield)

[00122] Synthesis of Compound 1: Anhydrous DMF (10 mL) was purged with N2 and then transferred via a cannula into a three-neck round bottomed flask charged with 1, 3, 5-tribromobenzene (1.00 g, 3.17 mmol) and bis (pinacolato) diboron (2.54 g, 9.53 mmol) . Potassium acetate (1.87 g, 19.0 mmol) and Pd(dppf)Cl₂ (0.087 g, 0.12 mmol) were then quickly added into the flask. The resulting mixture was stirred vigorously and heated at 90 °C for 24 hours. After cooling down to room temperature, deionized water (120 mL) was added. Black precipitate was collected by filtration, and washed with deionized water three times, which was dried under vacuum (98% yield) .

[00123] Synthesis of Compound 2: A mixture of compound 1 (0.79 g, 1.7 mmol) and methyl 2-amion-4-bromon-benzoate (1.35 g, 5.88 mmol) was dissolved in 48 mL mixed solvent of p-dioxane/lH O (1:1 v/v), which was deoxygenated by three freeze-pump-thaw cycles and protected under N2 atmosphere. After quickly adding of CsF (2.40 g, 15.7 mmol) and Pd(dppf) Cl2 (0.095 g, 0.13 mmol), the suspension was heated and stirred vigorously at 90 °C for 24 hours. After cooling down to room temperature, the resulting suspension was added with 150 mL of 20% NH4CI solution, and extracted three times with 3 ^χ 50 mL EtOAc using a 250-mL separatory funnel. The organic layers were combined, washed with saturated brine, dried with anhydrous Na2S04 and filtered. A crude product was obtained after removing all the solvent by rotary evaporation, and further purified by quick chromatography using CH2Cl2/EtOAc (15:1 v/v) as eluent (48% isolated yield) . 1H NMR (400 MHz, DMSO-d6, δ) : 7.85 (s, 3H, Ar H) , 7.83 (d, J = 8.4 Hz, 3H, Ar H) , 7.24 (s, 3H, Ar H) , 7.00 (d, J = 8.4 Hz, 3H, Ar H) , 6.75 (s, 6H, NH₂) , 3.82 (s, 9H, -COOCH3) .

[00124] Synthesis of linker B: Compound 2 (0.443 g, 0.840 mmol) was dissolved in 27 mL THF, added with 0.5 M NaOH aqueous solution

(27.0 mL, 13.5 mmol) . The suspension was stirred vigorously at 50 °C for 48 hours. After removing the THF by rotary evaporation, the aqueous solution was acidified with concentrated HCl to pH < 4. The white precipitation was collected by filtration, washed with deionized water, and dried under vacuum (96% yield) . 1H NMR (400 MHz, DMSO-c/6, δ) : 7.87 (s, 3H, Ar H) , 7.86 (d, J = 8.2 Hz, 3H, Ar H) , 7.35 (s, 3H, Ar H) , 7.12 (d, J = 8.4 Hz, 3H, Ar H) . ¹³C NMR (400 MHz, DMSO-d6, δ) : 169.02 (C=0) , 149.48 (C-NH₂) , 144.68, 140.90, 132.12, 124.91, 115.72, 115.42, 111.14, 109.2. ESI (m/ z) : [M - H]- calcd for C27H20N3O6- , 482.1358; found, 482.1346. ATR-FTIR (crrr¹) : 2918

(br), 1672 (s) , 1608 (m) , 1592 (m) , 1512 (w) , 1455 (w) , 1416 (w) , 1380 (m) , 1306 (w) , 1237 (w) , 1165 (s) , 1099 (w) , 1077 (w) , 1036

(w) , 961 (w) , 895 (w) , 860 (w) , 834 (w) , 774 (s) , 700 (w) , 674 (w) , 655 (w) , 644 (w) , 585 (w) , 555 (w) , 532 (w) .

[00125] Synthesis of Compound 3: A mixture of compound 1 (0.91g, 2.0 mmol) and methyl 2-methoxy-4-bromon-benzoate (1.6 g, 6.5 mmol) was dissolved in 48 mL mixed solvent of p-dioxane/lH O (1:1 v/v), which was deoxygenated by three freeze-pump-thaw cycles and protected under N₂ atmosphere. After quickly adding of CsF (2.7 g, 18 mmol) and Pd(dppf) Cl2 (0.11 g, 0.15 mmol), the suspension was heated and stirred vigorously at 90 °C for 24 hours. After cooling down to room temperature, the resulting suspension was added with 200 mL of 20% NH4CI solution, and extracted three times with 70 mL EtOAc using a 250-mL separatory funnel. The organic layers were combined, washed with saturated brine, dried with anhydrous Na2S04 and filtered. A crude product was obtained after removing all the solvent by rotary evaporation, and further purified by quick chromatography using CH2CI2 as eluent (54% isolated yield) .

[00126] Synthesis of linker D: Compound 3 (0.77 g, 1.5 mmol) was dissolved in 30 mL THF, added with 0.5 M NaOH aqueous solution (30 mL, 15 mmol) . The suspension was stirred vigorously at 50 °C for 48 hours. After removing the THF by rotary evaporation, the aqueous solution was acidified with concentrated HCl to pH < 2. The white precipitation was collected by filtration, washed with deionized water, and dried under vacuum (98% yield) . ^XH NMR (400 MHz, DMSO-d6, δ) : 12.6367(s, 3H, COOH) , 8.06 (s, 3H, Ar H) , 7.79 (d, J = 7.9 Hz, 3H, Ar H) , 7.53 (s, 3H, Ar H) , 7.51 (d, J = 8.1 Hz, 3H, Ar H) , 3.97

(s, 9H, -OMe ) . 13C NMR (400 MHz, DMSO-d6, δ) : 167.10 (COOH), 158.75

(C-OMe), 144.76, 144.02, 131.41, 125.86, 120.26, 119.12, 111.57, 56.07 ( -OCH3 ) . ESI (m/z) : [M - H] - calcd for C30H23O9-, 527.1348;

found, 527.1334. ATR-FTIR (cm-¹) : 3257 (m) , 2957 (w) , 2923 (w) , 2854

(w) , 1741 (s), 1608 (s) , 1565 (m) , 1499 (w) , 1455 (w) , 1437 (m) , 1393 (s), 1306 (w) , 1281 (w) , 1265 (m) , 1233 (m) , 1205 (m) , 1180

(m) , 1136 (m) , 1102 (w) , 1076 (m) , 1019 (s) , 935 (m) , 852 (m) , 833

(m) , 771 (m) , 749 (m) , 714 (w) , 679 (s) , 611 (w) , 553 (w) , 464 (w) . [00127] Synthesis of Compound 4: A mixture of compound 1 (0.91g, 2.0 mmol) and methyl 2 , 5-difluoro-4-bromon-benzoate (1.6 g, 6.5 mmol) was dissolved in 48 mL mixed solvent of p-dioxane/lH O (1:1 v/v) , which was deoxygenated by three freeze-pump-thaw cycles and protected under N₂ atmosphere. After quickly adding of CsF (2.7 g, 18 mmol) and Pd(dppf) Cl2 (0.11 g, 0.15 mmol), the suspension was heated and stirred vigorously at 90 °C for 24 hours. After cooling down to room temperature, the resulting suspension was added with 200 mL of 20% NH4CI solution, and extracted three times with 70 mL EtOAc using a 250-mL separatory funnel. The organic layers were combined, washed with saturated brine, dried with anhydrous Na2S04 and filtered. A crude product was obtained after removing all the solvent by rotary evaporation, and further purified by quick chromatography using ClH C^/Hexane (8:1 v/v) as eluent (55% isolated yield) .

[00128] Synthesis of linker F: Compound 4 (0.250 g, 0.425 mmol) was dissolved in 9 mL THF, added with 0.5 M NaOH aqueous solution

(9.0 mL, 4.5 mmol) . The suspension was stirred vigorously at 50 °C for 24 hours. After removing the THF by rotary evaporation, the aqueous solution was acidified with concentrated HCl to pH < 2. The white precipitation was collected by filtration, washed with deionized water, and dried under vacuum (98% yield) . ¹H NMR (400 MHz, DMSO-d6, δ) : 8.24 (s, 3H, Ar H) , 8.00 (s, 3H, Ar H) , 7.98 (s, 3H, Ar H) . 13C NMR (400 MHz, DMSO-d6, δ) : 162.19 (COOH) , 161.15 (C- F) , 158.65, 143.87, 126.30, 111.00. ESI (m/ z) : [M - H]^" calcd for C27Hii0₆F₆-, 545.0465; found, 545.0452. ATR-FTIR (crrr¹) : 3515 (w) , 2921

(m) , 2853 (w) , 2641 (br) , 1738 (s) , 1623 (s) , 1563 (s) , 1497 (w) , 1455 (m) , 1429 (w) , 1390 (s) , 1332 (m) , 1246 (m) , 1227 (m) , 1188

(s), 1116 (m) , 1074 (w) , 1038 (s) , 976 (m) , 902 (w) , 841 (s) , 785

(m) , 764 (m) , 737 (m) , 703 (w) , 625 (m) , 586 (w) , 572 (m) , 528 (m) , 506 (w) , 432 (w) .

[00129] Synthesis of Compound 6: A mixture of compound 1 (0.91g, 2.0 mmol) and methyl 2-fluoro-4-bromon-benzoate (1.6 g, 6.5 mmol) was dissolved in 48 mL mixed solvent of p-dioxane/H20 (1:1 v/v), which was de-oxygenated by three freeze-pump-thaw cycles and protected under N₂ atmosphere. After quickly adding of CsF (2.7 g, 18 mmol) and Pd(dppf) Cl2 (0.11 g, 0.15 mmol), the suspension was heated and stirred vigorously at 90 °C for 24 hours. After cooling down to room temperature, the resulting suspension was added with 200 mL of 20% NH4CI solution, and extracted three times with 70 mL EtOAc using a 250-mL separatory funnel. The organic layers were combined, washed with saturated brine, dried with anhydrous Na2S04 and filtered. A crude product was obtained after removing all the solvent by rotary evaporation, and further purified by quick chromatography using ClH C^/Hexane (8:1 v/v) as eluent (55% isolated yield) . ¹E NMR (400 MHz, DMSO-d6, δ) : 8.17 (s, 3H, Ar H) , 8.05 (d, J = 12.0 Hz, 3H, Ar H) , 7.95 (m, 6H, Ar H) , 3.90 (s, 9H, -COOCH3) .

[00130] Synthesis of linker H: Compound 6 (0.250 g, 0.425 mmol) was dissolved in 9 mL THF, added with 0.5 M NaOH aqueous solution

(9.0 mL, 4.5 mmol) . The suspension was stirred vigorously at 50 °C for 24 hours. After removing the THF by rotary evaporation, the aqueous solution was acidified with concentrated HCl to pH < 2. The white precipitation was collected by filtration, washed with deionized water, and dried under vacuum (98% yield) . ¹H NMR (400 MHz, DMSO-d6, δ) : 13.31 (s, 3H, COOH) , 8.17 (s, 3H, Ar H) , 8.00 (dd, J =11.9 Hz, 3H, Ar H) , 7.95 (d, J = 7.9 Hz , 3H, Ar H) , 7.89 (dd, J = 8.2 Hz, 3H Ar H) . ¹³C NMR (400 MHz, DMSO-d6, δ) : 164.91 (COOH), 162.53, 160.79, 132.34, 123.13, 115.72, 115.56, 145.65 (m) 139.41, 126.14, 118.27, 118.34. ESI {ml z) : [M - H]^" calcd for C27Hi₄F₃06^~, 491.0748; found, 491.0738. ATR-FTIR (cr¹) : 2920 (w) , 2661 (w) , 2548

(w) , 1692 (s), 1616 (s) , 1564 (m) , 1506 (w) , 1454 (m) , 1417 (m) , 1394 (m) , 1290 (m) , 1249 (m) , 1205 (m) , 1183 (m) , 1151 (m) , 1101

(m) , 1101 (m) , 1070 (m) , 957 (m) , 899 (m) , 864 (m) , 835 (m) , 774

(s), 759 (s), 692 (m) , 638 (w) , 593 (w) , 553 (m) , 496 (w) , 453 (m) , 412 (w) .

[00131] Synthesis of Compound 7: A mixture of compound 1 (0.91g, 2.0 mmol) and methyl 2-methyl-4-bromon-benzoate (1.6 g, 6.5 mmol) was dissolved in 48 mL mixed solvent of p-dioxane/H20 (1:1 v/v), which was de-oxygenated by three freeze-pump-thaw cycles and protected under N₂ atmosphere. After quickly adding of CsF (2.7 g, 18 mmol) and Pd(dppf)Cl2 (0.11 g, 0.15 mmol), the suspension was heated and stirred vigorously at 90 °C for 24 hours. After cooling down to room temperature, the resulting suspension was added with 200 mL of 20% NH4CI solution, and extracted three times with 70 mL EtOAc using a 250-mL separatory funnel. The organic layers were combined, washed with saturated brine, dried with anhydrous Na2S04 and filtered. A crude product was obtained after removing all the solvent by rotary evaporation, and further purified by quick chromatography using ClH C^/Hexane (8:1 v/v) as eluent (55% isolated yield) . ¹H NMR (400 MHz, CDC1₃, δ) : 8.05 (d, J = 8.0 Hz, 3H, Ar H) , 7.82 (s, 3H, Ar H) , 7.56 (m, 6H, Ar H) , 3.93 (s, 9H, -COOCH3) , 2.71 (s, 9H, -CH₃) .

[00132] Synthesis of linker I: Compound 7 (0.250 g, 0.425 mmol) was dissolved in 9 mL THF, added with 0.5 M NaOH aqueous solution

(9.0 mL, 4.5 mmol) . The suspension was stirred vigorously at 50 °C for 24 hours. After removing the THF by rotary evaporation, the aqueous solution was acidified with concentrated HCl to pH < 2. The white precipitation was collected by filtration, washed with deionized water, and dried under vacuum (97% yield) . ¹H NMR (400 MHz, DMSO-d6, δ) : 12.85 (s, 1H, COOH) , 8.03(s, 3H, Ar H) , 7.96 (d, J = 8.3 Hz, 3H, Ar H) , 7.85 (s, 3H, Ar H) , 7.81 (d, J = 8.2 Hz, 3H, Ar) , 2.65 (s, 9H, CH₃) . ¹³C NMR (400 MHz, DMSO-d6, δ) : 168.46 (COOH), 142.82, 140.66, 140.02, 131.02, 130.29, 129.50, 125.32, 124.63, 21.47(CH₃) . [M - H]- calcd for C₃oH₂30₆ ^~, 479.1500; found, 479.1490. ATR-FTIR (cm^"1) : 3257 (m) , 2957 (w) , 2923 (w) , 2854 (w) , 1741 (s), 1608 (s), 1565 (m) , 1499 (w) , 1455 (w) , 1437 (m) , 1393 (s) , 1306

(w) , 1281 (w), 1265 (m) , 1233 (m) , 1205 (m) , 1180 (m) , 1136 (m) , 1102 (w) , 1076 (m) , 1019 (s) , 935 (m) , 852 (w) , 833 (m) , 771 (m) , 749 (m) , 714 (w) , 679 (s) , 611 (w) , 553 (w) , 464 (w) .

[00133] Scheme 4 provides an example of the synthesis of the ester form of 1 , 3 , 5-tris ( 2 ' -amino-4 ' carboxyphenyl ) benzene .

8

Scheme 4 [00134] Synthesis of Compound 8: A mixture of methyl-4-iodo-3- nitrobenzoate (10 g, 33 mmol) , Pd(AcO)₂ (75 mg, 0.22 mmol) , (Bu) 4NBr

(125 mg) , and K₃P0₄ (13.5 g) in THF (300 mL) was added to 1 (5.0 g, 11 mmol) . The mixture was refluxed at 70 °C for 48 h under argon atmosphere. The solution was filtered through Celite and the filtered solution was evaporated. Purification of the crude product by flash column chromatography on silica gel (fourth spot,

hexane:EtOAc = 3:2, i?f = 0.35) provided pale yellow powders (3.0 g, 46% yield). ^XH NMR (DMSO-d<5, 400 MHz, δ) : 8.51 (s, 3H) , 8.30 (d, 3H, J = 8.0 Hz), 7.78 (d, 3H, J = 8.0Hz), 7.58 (s, 3H) , 3.94 (s, 9H) . ¹³C NMR (DMSO-d<5, 400 MHz, δ) : 164.8, 148.8, 138.7, 137.8, 133.7, 133.6, 130.9, 128.0, 125.5, 53.4. FT-IR (KBr, crrr¹) 3488 (br) , 3086 (w) , 2955 (w) , 2850 (w) , 1729 (vs) , 1619 (m) , 1534 (vs) , 1437 (m) , 1355

(m) , 1289 (s), 1260 (m) , 1194 (w) , 1152 (w) , 1119 (m) , 980 (w) , 905

(w) , 855 (w) , 824 (w) , 813 (w) , 759 (m) , 708 (w) , 416 (w).

[00135] Synthesis of Compound 9: A solution of 8 (2.7 g, 4.3 mmol) in acetic acid (100 mL) was added to Fe powder (3.6 g, 65 mmol) . The mixture was stirred at room temperature for 20 h under argon atmosphere. The solution was filtered through Celite and the filtered solution was evaporated. The residue was dissolved in EtOAc and H20. The organic layer was washed with a saturated NaHC03 (aq.) and brine, dried over MgS04, and filtered. The solvent was removed by rotary evaporation, yielding ivory powders (2.2 g, 97% yield) . ¹H-NMR (DMSO-d6, 400 MHz, δ) : 7.48 (s, 3H) , 7.43 (s, 3H) , 7.25 (d, 3H, J = 8.0 Hz), 7.21 (d, 3H, J = 8.0Hz), 5.33 (s, 6H) , 3.83 (s, 9H) . ¹³C NMR (DMSO-d<5, 400 MHz, δ) : 167.0 146.3 140.2 130.9 130.0 129.9 128.2 117.5 116.1 52.4. FT-IR (KBr, cm^"1): 3450 (m) , 3427 (m) , 3371 (m) , 3001 (w), 2951 (w) , 2848 (w) , 1718 (vs) , 1626 (m) , 1591

(w) , 1571 (w) , 1508 (w) , 1439 (m) , 1403 (w) , 1298 (s) , 1248 (m) , 1226 (m) , 1147 (w) , 1113 (m) , 1060 (w) , 996 (w) , 892 (w), 866 (w) , 763 (m) , 412 (w) .

[00136] Synthesis of linker J: A solution of 9 (4.0 g, 7.6 mmol) in a mixture of aqueous LiOH -H20 (0.6 M, 120 mL) , THF (120 mL) , and MeOH (60 mL) was stirred at room temperature for 20 h. After evaporation, the residue was acidified with 1M HC1 (< 72 mL) . The precipitate was filtered, washed with ¾0, and dried under vacuum to give ivory solids. ^XH NMR (400 MHz, DMSO-d6, δ) : 12.69 (s, 3H, COOH) , 7.47 (s, 3H, Ar H) , 7.40 (s, 3H, Ar H) , 7.21 (m, 6H, Ar H) , 5.26 (s, 6H, -NH₂) . ¹³C NMR (400 MHz, DMSO-d6, δ) : 167.69 (COOH), 145.62, 139.86, 130.82, 130.26, 129.31, 127.74, 117.41, 116.05. ESI:

[M - H] - calcd for C27H₂oN₃06^~, 482.1358; found, 482.1347. ATR-FTIR

(cm-¹) :3408 (w) , 3363 (w) , 3329 (w) , 3296 (w) , 2736 (br) , 2614 (br) , 1707 (m) , 1634 (m) , 1584 (m) , 1532 (w) , 1502 (w) , 1444 (m) , 1396

(m) , 1333 (m) , 1301 (m) , 1254 (w) , 1226 (m) , 1198 (s) , 1122 (m) , 1083 (m) , 1057 (w) , 997 (w),967 (m) , 943 (w) , 919 (m) , 901 (m) , 885

(m) , 849 (w) , 800 (m) , 766 (s) , 742 (s) , 729 (m) , 715 (m) , 677 (m) , 653 (m) , 630 (m) , 563 (m) , 502 (w) , 471 (m) .

[00137] Scheme 5 provides an example of the syntheses of the ester form of a hetero-functionlized BTB derivative based on multiple steps of Suzuki-Miyaura cross-coupling reaction.

12 (Sg&yfefct)

Scheme 5

[00138] Synthesis of compound 10: p-Dioxane/H20 solution (18 mL, 8:1 v: v) was purged with N2 and then transferred via a cannula into a three-neck round bottomed flask which was charged with a (510 mg, 1.62 mmol) and b (339 mg, 1.29 mmol) . CsF (588 mg, 3.87 mmol) and PdCl2 (dppf ) (23.4 mg, 0.0320 mmol) were then quickly added into the flask. The resulting mixture was stirred vigorously and heated at 90 °C for 24 hours. After cooling down to room temperature, 250 mL of 20% NH4CI solution was added into the mixture. The product was extracted by using 70 mL EtOAc three times. The organic layers were combined, washed with saturated brine, and dried with anhydrous MgS04. After filtration, the solvent was removed, and the crude product was further purified by quick chromatography using CH2C12 as eluent (43% yield) . ^XH NMR (400 MHz, DMSO-d6, δ) : 8.03 (d, J = 8.7 Hz, 2H, Ar H) , 7.98 (d, J = 1.7 Hz, 2H, Ar H) , 7.90 (m, 3H, Ar H) , 3.88 (s, 3H, -COOCH3) .

[00139] Synthesis of compound 11: p-Dioxane/H20 solution (18 mL, v: v = 8:1) was purged with N2 and then transferred via a cannula into a three-neck round bottomed flask which was charged with 10

(402 mg, 1.08 mmol) and c (293 mg, 0.939 mmol) . CsF (428 mg, 2.88 mmol) and PdCl2 (dppf ) (17.0 mg, 0.024 mmol) were then quickly added into the flask. The resulting mixture was stirred vigorously and heated at 90 °C for 24 hours. After cooling down to room

temperature, 150 mL of 20% NH4CI solution was added into the mixture. The product was extracted by using 40 mL EtOAc three times. The organic layers were combined, washed with saturated brine, and dried with anhydrous MgS04. After filtration, the solvent was removed, and the crude product was further purified by quick chromatography using CH2Cl2/EtOAc (12:1 v/v) as eluent (40% yield) . ¾ NMR (400 MHz, DMSO-d6, δ) : 8.83 (d, J = 8.8 Hz, 1H, Ar H) , 8.19

(d, J = 7.8 Hz, 1H, Ar H) , 8.10 (t, 1H, Ar H) , 8.04 (d, J = 8.6 Hz, 2H, Ar H) , 7.96 (d, J = 8.6 Hz, 2H, Ar H) , 7.88 (d, J = 8.1 Hz, Ar H) , 7.85 (t, 1H, Ar H) , 7.75 (t, 1H, Ar H) , 7.71 (m, 1H, Ar H) , 7.63

(m, 2H, Ar H) , 3.98 (s, 3H, -COOCH3) , 3.88 (s, 3H, -COOCH3) .

[00140] Synthesis of compound 12: p-Dioxane/H20 solution (9 mL, 8:1 v: v) was purged with N2 and then transferred via a cannula into a three-neck round bottomed flask which was charged with 11 (200 mg, 0.42 mmol) and d (212 mg, 0.530 mmol) . CsF (190 mg, 1.26 mmol) and PdCl2 (dppf ) (15.24 mg, 0.021 mmol) were then quickly added into the flask. The resulting mixture was stirred vigorously and heated at 90 °C for 24 hours. After cooling down to room temperature, 80 mL of 20% NH4CI solution was added into the mixture. The product was extracted by using 30 mL EtOAc three times. The organic layers were combined, washed with saturated brine, and dried with anhydrous MgS04. After filtration, the solvent was removed, and the crude product was further purified by quick chromatography using 2:1 Hexane/EtOAc as eluent (96% yield) . ^XH NMR (400 MHz, DMSO-d6, δ) : 8.87 (d, J = 9.0 Hz, 1H, Ar H) , 8.23 (d, J = 7.5 Hz, 1H, Ar H) , 8.10

(t, 1H, Ar H) , 8.08 (d, J = 8.6 Hz, 2H) , 8.03 (d, J = 8.7 Hz, 2H) , 7.97 (d, J = 8.1 Hz, 1H, Ar H) , 7.88 (t, 1H, Ar H) , 7.81 (d, J = 8.5 Hz, 1H, Ar H) , 7.77 (t, 1H, Ar H) , 7.75-7.61 (m, 4H, Ar H) , 7.28 (s, 1H, Ar H) , 7.07 (d, J = 8.7 Hz, 1H, Ar H) , 6.71 (s, 2H, -NH₂) , 3.99

(s, 3H, -COOCH3), 3.89 (s, 3H, -COOCH3) , 3.82 (s, 3H, -COOCH3) .

[00141] Synthesis of linker K: A NaOH aqueous solution (9.00 mL, 4.56 mmol) was added into 9 mL THF solution of 12 in (226 mg, 0.415 mmol) . Then the mixture was stirred vigorously at 65 °C for 24 hours. After cooling down to room temperature, the THF was removed by rotary evaporation, and the aqueous solution was acidified with concentrated HCl to pH < 2. The white precipitation was collected by filtration, washed with deionized water, and dried under vacuum (87% yield) . ¹E NMR (400 MHz, DMSO-d6, δ) : 12.97 (br, 3H, -COOH) , 8.51

(d, J = 8.8 Hz, 1H, Ar H) , 7.70 (d, J = 7.7 Hz, 1H, Ar H) , 7.62-7.35

(m, 6H, Ar H) , 7.31 (s, 1H, Ar H) , 7.25 (d, J = 8.3 Hz, 1H, Ar H) , 7.19 (s, 1H, Ar H) , 7.14 (t, J = 5.9 Hz, 2H, Ar H) , 7.06-7.00 (m, 1H, Ar H) , 6.64 (s, 1H, Ar H) , 6.43 (d, J = 8.6 Hz, 1H, Ar H) . ¹³C NMR (400 MHz, DMSO-d6, δ) : 169.37 (COOH), 168.67 (COOH), 167.14

(COOH), 151.82, 144.38, 143.75, 143.43, 140.95, 140.69, 140.19, 132.05, 131.41, 131.16, 130.01, 129.19, 127.92, 127.34, 126.84, 126.26, 125.88, 124.86, 114.50, 113.80, 109.22. ESI (m/ z) : [M - H]- calcd for C₃iH₂oN0₆ ^~, 502.1296; found, 502.1283. ATR-FTIR (crrr¹) : 3487

(w) , 3368 (w) , 2923 (w) , 2633 (vw) , 2536 (w) , 1678 (s) , 1609 (m) , 1591 (m) , 1548 (m) , 1514 (m) , 1450 (w) , 1412 (m) , 1381 (m) , 1282

(m) , 1234 (s), 1143 (w) , 1106 (m) , 1016 (w) , 964 (w) , 892 (w) , 851

(m) , 772 (s), 704 (m) , 667 (w) , 643 (w) , 573 (w) , 537 (w) , 463 (w) , 443 (w) .

[00142] Characterization of linker C: ^XH NMR (400 MHz, DMSO-d6, δ) : 8.61 (s, 3H, Ar H) , 8.41 (d, J = 7.6 Hz, 3H, Ar H) , 8.33 (s, 3H, Ar H) , 8.02 (d, J = 8.1 Hz, 3H, Ar H) . ¹³C NMR (400 MHz, DMSO-d6, δ) : 165.34 (COOH), 149.79, 143.43, 138.76, 131.10, 130.73, 126.82, 125.32, 122.11. ESI {ml z) : [M - H]- calcd for C27H14N3O12- , 572.0583; found, 572.0564. ATR-FTIR (cm-¹) : 3504 (br) , 3080 (br) , 1686 (m) , 1614 (m) , 1560 (w) , 1528 (s) , 1502 (m) , 1450 (w) , 1398 (m) , 1353

(s), 1227 (s), 1146 (m) , 1110 (w) , 1057 (m) , 977 (w) , 927 (w) , 908

(w) , 881 (m) , 845 (m) , 820 (m) , 771 (m) , 748 (m) , 693 (m) , 645 (m) , 579 (m) , 522 (w) , 484 (w) , 466 (w) , 452 (w) , 432 (w) .

[ 00143 ] Characterization of linker E: ^XH NMR (400 MHz, DMSO-d6, δ) : 7.97 (s, 3H, Ar H) , 7.81 (d, J = 7.8 Hz, 3H, Ar H) , 7.61 (s, 3H, Ar H) , 7.57 (d, J = 7.3 Hz, 6H, Ar H) , 7.50 (d, J = 8.1 Hz, 3H, Ar H) , 7.39 (m, 6H, Ar H) , 7.31 (m, 6H Ar H) , 5.40 (s, 6H) . ¹³C NMR (400 MHz, DMSO-d6, δ) : 167.30 (COOH) , 157.48, 144.21, 140.92, 137.22, 131.30, 128.35, 127.61, 127.16, 119.35, 113.05, 69.8. ESI: [M - H]- calcd for C48H₃509^~, 755.2287; found, 755.2271. ATR-FTIR (cm-1) : 3245

(w) , 3032 (w) , 2974 (w) , 1718 (s) , 1687 (m) , 1604 (s) , 1562 (m) , 1498 (m) , 1447 (m) , 1392 (s) , 1304 (m) , 1262 (m) , 1215 (m) , 1189

(s), 1138 (m) , 1101 (w) , 1074 (m) , 990 (m) , 910 (m) , 835 (m) , 767

(m) , 733 (s), 692 (s) , 626 (m) , 556 (w) , 485 (w) , 459 (w) .

[ 00144 ] Characterization of linker G: . ¹E NMR (400 MHz, DMSO-d6, δ) : 13.25 (s, 3H, COOH), 8.97 (d, J = 7.8 Hz, 3H, Ar H) , 8.22 (d, J = 7.8 Hz, 3H, Ar H) , 8.22 (d, J = 7.8 Hz, 3H, Ar H) , 7.78 (d, J = 7.8 Hz, 3H, Ar H) , 7.75 (s, 1H, Ar H) , 7.72-7.66 (m, 2H, Ar H) . ¹³C NMR (400 MHz, DMSO-d6, δ) : 168.59 (COOH), 143.03, 140.04, 131.29, 131.18, 130.49, 129.20, 127.90, 127.45, 126.84, 126.45, 126.02. ESI

(m/z) : [M - H]- calcd for C 39H23O6^" , 587.1500; found, 587.1480. ATR- FTIR (cm-¹) : 2920 (w) , 2852 (w) , 1676 (s) , 1574 (m) , 1512 (m) , 1462

(m) , 1421 (m) , 1374 (m) , 1312 (w) , 1282 (m) , 1249 (s) , 1193 (m) , 1165 (m) , 1139 (m) , 1037 (w) , 1037 (w) , 958 (w) , 891 (m) , 849 (m) , 794 (m) , 773 (s) , 718 (m) , 658 (w) , 642 (m) , 606 (w) , 544 (w) , 5114

(w) , 482 (w) , 464 (w) , 455 (w) , 428 (m) .

[ 00145 ] Synthesis of functionalized IRMOF-177 analogs. Crystals of IRMOF-177 were generally isolated from solvothermal reactions of Ζη(Ν03> 2 * 6¾0 and the acid form of a functionalized BTB linker in DEF, which are similar to the conditions previously used in the preparation of original MOF-177. To obtain highly crystalline samples and avoid contamination from isomeric phases of MOFs, reaction conditions of some IRMOF-177 analogs were slightly modified by changing the temperature, concentration, organic solvent, and so on .

[ 00146] IRMOF-177-B, Zn₄0 (BTB-NH₂) 2 : A mixture of H3BTB-NH2 (12 mg, 0.025 raraol; in 9.0 mL DEF) and Zn (N0₃) 2 * 6H₂0 (63 mg, 0.22 raraol; in 1.0 mL DEF) in a 20-mL vial was sonicated for 30 min and then heated in an isothermal oven at 85 °C for 48 hours. After decanting the mother liquor, yellow block crystals were isolated and washed three times with fresh DMF (10 mL) .

[ 00147 ] IRMOF-177-D, Zn₄0 (BTB-OMe) ₂: A mixture of H₃BTB-OMe(53 mg, 0.10 raraol; in 9.0 mL DEF) and Zn (N0₃) 2 * 6H₂0 (250 mg, 0.84 raraol; in 1.0 mL DEF) in a 20-mL vial was sonicated for 30 min and then heated in an isothermal oven at 100 °C for 20 hours. After decanting the mother liquor, colorless block crystals were isolated and washed three times with fresh DMF (10 mL) .

[ 00148 ] IRMOF-177-E, Zn₄0 (BTB-OBn) ₂: A mixture of H₃BTB-OBn (76 mg, 0.10 ramol; in 9.0 mL DEF) and Zn (N0₃) 2 * 6H₂0 (250 mg, 0.84 raraol; in 1.0 mL DEF) in a 20-mL vial was sonicated for 30 min and then heated in an isothermal oven at 100 °C for 20 hours. After decanting the mother liquor, colorless block crystals were isolated and washed three times with fresh DMF (10 mL) .

[ 00149 ] IRMOF-177-F, Zn₄0 (BTB-6F) ₂: A mixture of H₃BTB-6F (27 mg, 0.050 raraol; in 9.0 mL DEF) and Zn (N0₃) 2 * 6H₂0 (125 mg, 0.42 raraol; in 1.0 mL DEF) in a 20-mL vial was sonicated for 30 min and then heated in an isothermal oven at 85 °C for 48 hours. After decanting the mother liquor, colorless hexagonal crystals were isolated and washed three times with fresh DMF (10 mL) .

[ 00150 ] IRMOF-177-G, Zn₄0 (BTB-Nap) 2 '· A mixture of H₃BTB-Nap

(59 mg, 0.10 raraol; in 9.0 mL DEF) and Zn (N0₃) 2 * 6H₂0 (250 mg, 0.84 ramol; in 1.0 mL DEF) in a 20-mL vial was sonicated for 30 min and then heated in an isothermal oven at 100 °C for 20 hours. After decanting the mother liquor, colorless block crystals were isolated and washed three times with fresh DMF (10 mL) .

[ 00151 ] IRMOF-177-H, Zn₄0 (BTB-3F) 2 '· A mixture of H₃BTB-3F (25 mg, 0.050 raraol; in 9.0 mL DEF) and Zn (N0₃) 2 * 6H₂0 (125 mg, 0.42 raraol; in 1.0 mL DEF) in a 20-mL vial was sonicated for 30 min and then heated in an isothermal oven at 85 °C for 48 hours. After decanting the mother liquor, colorless block crystals were isolated and washed three times with fresh DMF (10 mL) .

[00152] IRMOF-177-I, Zn₄0 (BTB-Me) ₂: The mixture of H₃BTB-Me (24 mg, 0.050 ramol; in 9.0 mL DEF) and Zn (N0₃) 2 * 6H₂0 (125 mg, 0.42 ramol; in 1.0 mL DEF) in a 20-mL vial was sonicated for 30 min and then heated in an isothermal oven at 85 °C for 48 hours. After decanting the mother liquor, colorless block crystals were isolated and washed three times with fresh DMF (10 mL) .

[00153] IRMOF-177-J, Zn₄0 (BTB-mNH₂) 2: A mixture of H₃BTB-mNH₂ (48 mg, 0.1 ramol; in 9.0 mL DMF) and Zn (N0₃) 2 * 6H₂0 (250 mg, 0.84 ramol; in 1.0 mL DMF) in a 20-mL vial was sonicated for 30 min, and then heated in an isothermal oven at 100 °C for 20 hours. After decanting the mother liquor, yellow block crystals were isolated and washed three times with fresh DMF (10 mL) .

[00154] IRMOF-177-K, Zn₄0 (BTB-Nap-NH₂) 2: A mixture of H₃BTB-Nap-NH₂ (25 mg, 0.050 raraol; in 9.0 mL DEF) and Zn (N0₃) 2 * 6H₂0 (125 mg, 0.42 ramol; in 1.0 mL DEF) in a 20-mL vial was sonicated for 30 min and then heated in an isothermal oven at 100 °C for 20 hours. After decanting the mother liquor, yellow block crystals were isolated and washed three times with fresh DMF (10 mL) .

[00155] Isolation of MOF-177 isomers. During the screening of synthetic conditions for preparing IRMOF-177 analogs, several isomeric MOFs were isolated.

[00156] Isomeric MOF-BTB-6F with pyr-net, Zn₄0 (BTB-6F) ₂: A mixture of H₃BTB-6F (54 mg, 0.10 raraol; in 9.0 mL DEF) and Zn (N0₃) 2 * 6H₂0 (250 mg, 0.84 ramol; in 1.0 mL DEF) in a 20-mL vial was sonicated for 30 min and then heated in an isothermal oven at 100 °C for 20 hours. After decanting the mother liquor, yellow block crystals were isolated and washed three times with fresh DMF (10 mL) .

[00157] Isomeric M0F-BTB-mNH₂ with rtl-net, Zn₄0 (BTB-mNH₂) 2: A mixture of H₃BTB-mNH₂ (54 mg, 0.10 ramol; in 9.0 mL DEF) and Zn(N0₃)₂ * 6H₂0 (250 mg, 0.84 raraol; in 1.0 mL DEF) in a 20-mL vial was

sonicated for 30 min and then heated in an isothermal oven at 100 °C for 20 hours. After decanting the mother liquor, yellow block crystals were isolated and washed three times with fresh DMF (10 mL) . [ 00158 ] Synthesis of MTV MOF-177 variants. mtv-MOF-177 variants were synthesized though solvothermal reactions and isolated as single-crystal forms. The structural and physical characteristics of the multivariate MOFs are dependent upon the particular

combination of different kinds of linking ligands, and by the stoichiometric control of ratio of different linking ligands. MTV MOF-177 variants were synthesized with different combinations of BTB and functionalized BTB-based linkers. The ratio of BTB to

functionalized linker was also adjusted. Illustrated herein, is the synthesis and characterization of a binary MTV-MOF-177 having stoichiometric ratio of H₃BTB and H3BTB-6F of 1:1.

[ 00159 ] MTV-MOF-177-AG, ZnO (BTB) (BTB-6F) : H₃BTB (25 mg, 0.057 mmol) and H3BTB-6F (31 mg, 0.057 mmol) were dissolved with 9 mL DEF in a 20-mL vial, and then added with Zinc nitrate hexahydrate (250 mg, 0.84 mmol in 1 mL DEF) . The mixture was sonicated for 30 min, and then heat at 100 °C in an isothermal oven. Block colorless crystals were obtained after 16 hours.

[ 00160 ] Activation methods of MOF-177 analogs. Although MOF-177 can be full activated using the established protocol involving solvent-exchange and evacuation with heating, the supercritical CO2 drying (SCD) protocol is worth employing in the optimization activation due to the better performance in many ultrahigh surface area MOFs. In this study, different activation methods were tried and optimized using the rough uptake of N2, prior to taking the full adsorption measurement.

[ 00161 ] Established protocol: As-synthesized samples of MOF-177 analogs were immersed in chloroform or dichloromethane (15 mL in a 20-mL vial) for three days, during which time the solvent was decanted and freshly replenished three times per day. The suspension of crystals was then transferred to an adsorption cell using glass pipette to avoid direct exposure to humidity. After the removal of bulk solvent in the cell using syringe with a long, the sample was maintained in vacuo at room temperature for 2 hours. The sample was then heated to 100 °C using a constant rate of 2 °C/min over a period of 12 hours. The sample was cooled to room temperature and backfilled with Ar before taking the adsorption measurement. [ 00162 ] SCD protocol: As-synthesized samples of MOF-177 analogs were exchanged with acetone for three days, as indicated above.

Wrapping with Kimwipe® paper in an extraction thimble, the wet sample was transferred to the chamber of a Tousimis Samdri PVT-3D critical point dryer, where the MOFs were immersed in liquid CO2 and changed with fresh liquid CO2 for five times. After heating to 30-45 °C in order to reach the supercritical state, the sample was maintained at this temperature for a half hour, and the CO2 was bled off as gas at a rate of 2 mL/min. The sample was then transferred to sorption cell in a glovebox, and maintained in vacuo at room temperature for 12 hours before taking sorption measurements.

[ 00163 ] Isoreticular syntheses of functionalized MOF-177 analogs. As shown in FIG. 4A-I, all functionalized H3BTB derivatives, except the H3BTB-NO2 linker, can produce isoreticular frameworks with the expected qom topology of MOF-177. All the IRMOF-177 analogs possess the same octahedral inorganic SBU, Zn40(COO^") 6, linked by tritopic organic linkers to form the extended 3D frameworks. They differ in the linker conformation, nature of functional group decorating the pores, and in the metrics of their pore structure. IRMOF-177-B, -C, -F and -I comprise small sized functional groups. Their pore volumes were calculated from their structures to be around 1.70 cm³/g (see TABLE 1), which is slightly lower than that of MOF-177 (1.88 cm³/g) .

[ 00164 ] TABLE 1. Crystallographic information of IRMOF-177 analogs and calculated porosity behavior.

[ 00165 ] In the structure of IRMOF-177-I, the three branched benzene rings are perpendicular to the centered benzene, which can be attributed to the significant steric hindrance resulting from substitution at the X² position. A geometric calculation shows the accessible surface area of IRMOF-177-I to be around 4805 m²/g, which is greater than the other functionalized BTB-based analogs and MOF- 177 (4796 m²/g) . IRMOF-177-D, -F, and -K with slightly bulkier functional groups have a pore volume in the region 1.53-1.50 cm²/g; IRMOF-177-E and -G with very large bulky functional groups have the pore volume of 0.93 and 1.36, respectively. Although bulkier functional groups reduce pore volume, the polarization of pore surfaces and partitioning of pore size may enhance their adsorptive ability along with their higher surface area.

[ 00166] Troubleshooting with topological isomerization in reticular functionalization of MOF-177. The first syntheses of MOF- 177-F, resulted in the isolation of cubic shape crystals when using the general synthetic conditions. By comparing the PXRD patterns with MOF-177, these synthesized MOFs were of a different phase.

SCXRD analysis demonstrated that the synthesized MOFs had the same octahedral Zn40(COO^") 6 inorganic SBUs and the same connectivity of the BTB-6F linkers, but were in a doubly interpenetrating pyr net. Disregarding the solvents in the crystals, this MOF is a topological isomer to MOF-177-6F. The expected qom net was finally obtained by using lower temperatures and concentrations.

[ 00167 ] Needle crystals were obtained in the first trials to make MOF-177-J. Its single-crystal structure represents a 3D extended framework composed of the same Zn40(COO^") 6 SBU and the same BTB-mNlH linker, but resulted in the rtl net. The conformation of the BTB- mNH2 linker was different than the normal BTB linker, in that the two of the carboxylate groups have a large twist angle of 56° to the centered benzene ring, and one carboxylate group is in the same plane with the centered benzene ring. This MOF possesses high porosity with 80.0 % void, and a low framework density of 0.41 g/cm³. The pore volume (2.0 cm³/g) and accessible surface area (4918 m²/g) are also higher than MOF-177.

[ 00168 ] As shown in FIG. 5, there are several possible networks composed of alternating octahedron and triangle SBUs. The pyr net has been observed in the doubly interpenetrated MOF-150 with the 4 , 4 ' , 4 ' ' -nitrilotribenzoate (TCA) linker, but this is the first instance of a pyr net with a BTB-based ligand. The tsx and ant net were discovered in MOFs synthesized from the reaction of H3BTB with Zn (N0₃) 2 * 4H₂0 in DMF or DMF/EtOH/H₂0. These examples reveal that the frameworks are not only influenced by the geometries of SBUs, but also by linker conformation and synthesis conditions. Therefore, based upon the functionalization of the BTB-based linkers, the kinetics of crystal growth is affected, leading to different thermally dynamically stable forms. Examples of possible nets for MOFs using the BTB-based linking ligands disclosed herein are presented in TABLE 2.

[ 00169 ] TABLE 2. Possible nets of alternatively linked octahedron and triangle in the RCSR database .

[ 00170 ] High-symmetry structures are common to MOFs, which result from using geometric SBUs and the enumeration of periodic networks. However, structural uncertainty still remains when the MOFs are comprised of linking differently shaped SBUs. The phenomenon of supramolecular isomerism has attracted great interest in

coordination chemistry and crystal engineering. In particular, how ligand conformation affects supramolecular assembly and crystal growth. The disclosure therefore provides an opportunity to better understand the processes involved in forming different networks from the same components .

[ 00171 ] Systematical syntheses of MTV-MOF-177 variants. A series of MTV-MOF-177 variants were prepared. First prepared were the binary MTV-MOFs, which were formed by mixing the H₃BTB linker with functionalized BTB derivatives with varying linker stoichiometries . The resulting linker ratios in the crystals were characterized by solution NMR of digested samples (see TABLE 3 ) .

[ 00172 ] TABLE 3. Ratio of linkers in MTV-MOF-177 crystals of different combinations with varying reaction stoichiometries (ratios are shown in parentheses) determined by ID solution ¹H NMR

spectroscopy of the digested samples. In each case, the ratios were normalized to a value of one for linker A. N/A, not applicable; MP, mixed phases .

[ 00173 ] The disclosure illustrate the case of binary MTV-MOF-177- F series. As shown in FIG. 7B, when utilizing a H₃BTB-6F linker ratio of 8:2, mixed phases were observed at 85 °C. This phase separation problem was solved by using lower reaction temperatures. The output linker ratios of MTV-MOF-177-F in region with qom pure phase are consistent for both temperatures. The input-output ratio shows a bias curve, which may be attributed to the different pKa value, steric hindrance and coordination kinetics between the linkers .

[ 00174 ] Ternary MTV-MOF-177 variants were also prepared. FIG. 8 presents an analysis the linker ratio of MTV-MOF-177-ABG based upon a ID solution ^XH NMR spectrum of a digested sample (10 mg sample was dissolved in 600 DMSO-d₆ with 20 25% HC1 in D₂0) . The

overlapping multiple peaks at 8.05 ppm can all be assigned to the protons on the BTB linker, which have to be integrated together as one (for 15 protons) . The singlet at 7.60 ppm was assigned to proton g on the centered benzene ring of BTB-NH2; the doublet at 7.43 ppm (J = 7.9 Hz) was assigned to proton f next to the amino group; the multiplet at 7.93 ppm was assigned to proton d and e, which may have overlapping with that of DMF at 7.96 ppm marked with asterisk. The doublet at 8.93 ppm (J = 8.7 Hz) was assigned to proton i from BTB- Nap, multiplet at 8.19 ppm was assigned to proton n and k with overlapping; doublet at 7.76 ppm (J = 7.9 Hz) was assigned to proton j; singlet at 7.72 ppm was assigned to proton h, which is overlapped with pentalet of proton i and m at 7.68 ppm. The characteristic peak was selected without overlapping for integration, and the resulting ratio was calculated as 1:0.32:0.62 for BTB : BTB-NH₂ : BTB-Nap .

[ 00175 ] Permanent porosity and adsorption capacity. Permanent porosity of IRMOF-177 analogs was confirmed by N2 adsorption experiments at 77 K. All the examined analogs showed significant N2 uptake at low-pressure (P/Po < 0.05), whose profiles can be

classified as type I isotherms (See FIG. 15) . IRMOF-177-B and -I have the larger DR pore volume (1.63 and 1.68 cm³/g, respectively) than that of IRMOF-D and -F (1.53 cm³/g for -F) . The BET surface areas of IRMOF-177-B, -D, -F and -I are 3800, 2330, 3688, and 3478 m²/g, respectively.

[ 00176] Permanent porosity of MTV-MOF-177 series was also

characterized by N2 adsorption experiments at 77 K. As shown in FIG. 16A, by varying the stoichiometry, the porosity of the MOFs can be modified. The H₂ uptake of MTV-MOF-177-AG (5:5) increased in comparison to MOF-177 and IRMOF-177-G (see FIG. 16B) .

[ 00177 ] A number of embodiments have been described herein.

Nevertheless, it will be understood that various modifications may be made without departing from the spirit and scope of this disclosure. Accordingly, other embodiments are within the scope of the following claims.

Claims

WHAT IS CLAIMED IS:

1. A metal organic framework (MOF) that comprises a plurality SBUs that are linked together by a plurality of 1, 3, 5-tris (4- carboxyphenyl ) benzene (BTB) -based linking ligands comprising the structure of Formula I :

Formula (I)

wherein the carboxylic acid groups in Formula I, undergo

condensation with the SBU, and wherein:

A¹-A³ are independently a C or N;

R^x-R¹² are independently selected from H, D, FG, optionally substituted (C1-C12) alkyl, optionally substituted hetero- (C1-C12) alkyl, optionally substituted (C1-C12) alkenyl, optionally substituted hetero- (C1-C12) alkenyl, optionally substituted (C1-C12) alkynyl, optionally substituted hetero- (C1-C12) alkynyl, optionally substituted (C1-C12) cycloalkyl, optionally substituted (C1-C12) cycloalkenyl, optionally substituted aryl, optionally substituted heterocycle, optionally substituted mixed ring system, -C(R¹³) 3, -CH(R¹³)₂, -CH₂R¹³, -C(R¹⁴)₃, -CH(R¹⁴)₂, -CH2R¹⁴, -OC(R¹³)₃, OCH(R¹³)₂, -OCH₂R¹³, -OC(R¹⁴)₃, - OCH(R¹⁴)2, OCH2R¹⁴, wherein R^x-R¹² when adjacent can be linked together to form one or more optionally substituted rings selected from the group comprising cycloalkyl, cycloalkenyl, heterocycle, aryl, and mixed ring system;

(C1-C12) alkenyl, optionally substituted hetero- (C1-C12) alkenyl, optionally substituted (C1-C12) alkynyl, optionally substituted hetero- (Ci- C12) alkynyl, hemiacetal, hemiketal, acetal, ketal, and orthoester ;

R¹⁴ is selected from one or more substituted or unsubstituted rings selected from cycloalkyl, aryl and heterocycle ; and

wherein when A¹-A³ are C and R^x-R¹² are H, the MOF further comprises a linking ligand comprising the structure of Formula I where at least one of R^x-R¹² are not H when A¹-A³ are C.

2. The MOF of claim 1, wherein the BTB-based linking ligand comprises the structure of Formula I :

Formula I

wherein,

A¹-A³ are independently a C or N;

x-R¹² are independently selected from:

79

M is an alkaline metal species, an alkaline-earth metal species, or transition metal species that has a formal charge of +1 and that can be coordinated by one or more neutral or charged ligands .

3. The MOF of any preceding claim, wherein the BTB-based linking ligand comprises the structure of:

4. The MOF of any preceding claim, wherein the MOF is multivariate by comprising two or more different BTB-based linking ligands comprising the structure of Formula I :

Formula (I)

wherein,

A¹-A³ are independently a C or N;

R^x-R¹² are independently selected from H, D, FG, optionally substituted (C1-C12) alkyl, optionally substituted hetero- (C1-C12) alkyl, optionally substituted (C1-C12) alkenyl, optionally substituted hetero- (C1-C12) alkenyl, optionally substituted (C1-C12) alkynyl, optionally substituted hetero- (Ci- C12) alkynyl, optionally

substituted (C1-C12) cycloalkyl, optionally substituted (Ci- C12) cycloalkenyl, optionally substituted aryl, optionally substituted heterocycle, optionally substituted mixed ring system, -C(R¹³) 3, - CH(R¹³)₂, -CH2R¹³, -C(R¹⁴)₃, -CH(R¹⁴)₂, -CH2R¹⁴, -OC(R¹³)₃, OCH(R¹³)₂, - OCH₂R¹³, -OC(R¹⁴)₃, -OCH(R¹⁴)₂, OCH₂R¹⁴, wherein R^x-R¹² when adjacent can be linked together to form one or more optionally substituted rings selected from the group comprising cycloalkyl, cycloalkenyl, heterocycle, aryl, and mixed ring system;

R¹³ is selected from FG, optionally substituted (C1-C12) alkyl, optionally substituted hetero- (C1-C12) alkyl, optionally substituted (C1-C12) alkenyl, optionally substituted hetero- (C1-C12) alkenyl, optionally substituted (C1-C12) alkynyl, optionally substituted hetero- (Ci- C12) alkynyl, hemiacetal, hemiketal, acetal, ketal, and orthoester ;

R¹⁴ is selected from one or more substituted or unsubstituted rings selected from cycloalkyl, aryl and heterocycle.

5. The MOF of claim 4, wherein the two or more different BTB-based linking ligands are selected from the group consisting of:

86

6. The MOF of claim 4 or claim 5, wherein the two or more

different BTB-based linking ligands comprise a stoichiometric ratio of 1:10 to 10:1.

7. The MOF of any preceding claim, wherein the plurality of SBUs comprise one or more metals or metal ions selected from: Li⁺, Na⁺, K⁺, Rb⁺, Cs⁺, Be²⁺, Mg²⁺, Ca²⁺, Sr²⁺, Ba²⁺, Sc³⁺, Sc²⁺, Sc⁺, Y³⁺, Y²⁺, Y⁺,

Ti⁴⁺, Ti³⁺, Ti²⁺, Zr⁴⁺, Zr³⁺, Zr²⁺ , Hf⁴⁺, Hf³⁺, V⁵⁺, V⁴⁺, V³⁺, V²⁺, Nb⁵⁺, Nb⁴⁺,

Nb³⁺, Nb²⁺, Ta⁵⁺, Ta⁴⁺, Ta³⁺, Ta²⁺ , Cr⁶⁺, Cr⁵⁺, Cr⁴⁺, Cr³⁺, Cr²⁺, Cr⁺, Cr,

Mo⁶⁺, Mo⁵⁺, Mo⁴⁺, Mo³⁺, Mo²⁺, Mo⁺, Mo, W⁶⁺, W⁵⁺, W⁴⁺, W³⁺, W²⁺, W⁺, W, Mn⁷⁺,

Mn⁶⁺, Mn⁵⁺, Mn⁴⁺, Mn³⁺, Mn²⁺, Mn⁺, Re⁷⁺, Re⁶⁺, Re⁵⁺, Re⁴⁺, Re³⁺, Re²⁺, Re⁺,

Re, Fe⁶⁺, Fe⁴⁺, Fe³⁺, Fe²⁺, Fe⁺, Fe, Ru⁸⁺, Ru⁷⁺, Ru⁶⁺, Ru⁴⁺, Ru³⁺, Ru²⁺,

Os⁸⁺, Os⁷⁺, Os⁶⁺, Os⁵⁺, Os⁴⁺, Os³⁺ , Os²⁺, Os⁺, Os, Co⁵⁺, Co⁴⁺, Co³⁺, Co²⁺,

Co⁺, Rh⁶⁺, Rh⁵⁺, Rh⁴⁺, Rh³⁺, Rh²⁺, Rh⁺, Ir⁶⁺, Ir⁵⁺, Ir⁴⁺, Ir³⁺, Ir²⁺, Ir⁺,

Ir, Ni³⁺, Ni²⁺, Ni⁺, Ni, Pd⁶⁺, Pd⁴⁺, Pd²⁺, Pd⁺, Pd, Pt⁶⁺, Pt⁵⁺, Pt⁴⁺, Pt³⁺, Pt²⁺, Pt⁺, Cu⁴⁺, Cu³⁺, Cu²⁺, Cu⁺, Ag³⁺, Ag²⁺, Ag⁺, Au⁵⁺, Au⁴⁺, Au³⁺, Au²⁺,

Au⁺, Zn²⁺, Zn⁺, Zn, Cd²⁺, Cd⁺, Hg⁴⁺, Hg²⁺, Hg⁺, B³⁺, B²⁺, B⁺, Al³⁺, Al²⁺,

Al⁺, Ga³⁺, Ga²⁺, Ga⁺, In³⁺, In²⁺, In¹⁺, Tl³⁺, Tl⁺, Si⁴⁺, Si³⁺, Si²⁺, Si⁺,

Ge⁴⁺, Ge³⁺, Ge²⁺, Ge⁺, Ge, Sn⁴⁺, Sn²⁺, Pb⁴⁺, Pb²⁺, As⁵⁺, As³⁺, As²⁺, As⁺,

Sb⁵⁺, Sb³⁺, Bi⁵⁺, Bi³⁺, Te⁶⁺, Te⁵⁺, Te⁴⁺, Te²⁺, La³⁺, La²⁺, Ce⁴⁺, Ce³⁺, Ce²⁺

Pr⁴⁺, Pr³⁺, Pr²⁺, Nd³⁺, Nd²⁺, Sm³⁺, Sm²⁺, Eu³⁺, Eu²⁺, Gd³⁺, Gd²⁺, Gd⁺, Tb⁴⁺,

Tb³⁺, Tb²⁺, Tb⁺, Db³⁺, Db²⁺, Ho³⁺, Er³⁺, Tm⁴⁺, Tm³⁺, Tm²⁺, Yb³⁺, Yb²⁺, Lu³⁺,

La³⁺, La²⁺, La⁺, and combinations thereof, including any complexes which contain the metals or metal ions, as well as any corresponding metal salt counter-anions .

8. The MOF of any preceding claim, wherein the plurality of SBUs comprise zinc metal ions, including any complexes which contain the zinc metal ions, as well as any corresponding metal salt counter- anions .

9. The MOF of any preceding claim, wherein the MOF comprises a qom, pyr or rtl net topology.

10. A device comprising a MOF of any one of the preceding claims.

11. The device of claim 10, wherein the device is a gas separation and/or gas storage device .

12. The device of claim 11, wherein the device comprises an

Absorbed Natural Gas (ANG) tank.

13. A vehicle comprising the device of claim 12.

14. A method of separating and/or storing one or more gases from a gas mixture comprising contacting the gas mixture with a MOF of any one of claims 1 to 9.

15. The method of claim 14, wherein the gas mixture is natural gas and the gas that is separated and/or stored is methane.

16. The method of claim 14, wherein the gas mixture comprises hydrogen and the gas that is separated and/or stored is hydrogen.