Crystal Engineering of a Microporous, Catalytically Active fcu Topology MOF Using a Custom‐Designed Metalloporphyrin Linker

Abstract

A major driving force behind the recent surge of interest in metal-organic frameworks (MOFs) [1] lies with their amenability to design using crystal engineering [2a-d] strategies. In particular, MOFs with specific composition and topology can be targeted by judicious selection of organic linkers and metal-based molecular building blocks [2e-g] (MBBs) that serve as nodes. [2] Furthermore, their modular nature means that prototypal MOFs can serve as blueprints or platforms for a plethora of derivatives with controlled pore size and surface area, as exemplified by the practice of "reticular synthesis". [3] Such features make MOFs stand out over traditional porous materials, and afford them with potential for use in gas storage, [4] separation, [5] CO 2 capture, [6] sensor, [7] catalysis, [8] and other areas. [9] High-symmetry MOFs based upon high-connectivity polyhedral cage MBBs that are in effect supermolecular building blocks (SBBs) can provide exquisite control over structure because of their high connectivity and also afford the features of confined nanospace [10] and extra-large surface area. [11] Such MOFs have afforded superior performance in the context of gas storage for hydrogen, methane, CO 2 , and other gas molecules. [4, 6, 11,12] The nature of the nanospace in SBB-based MOFs is such that they can encapsulate catalytically active species, for example, organometallics, [13] polyoxometallates, [14] metalloporphyrins (porph@MOMs), [15] and enzymes. [16] Along with encapsulation of catalysts, it is possible to generate porphyrin-walled MOFs by customdesigning metalloporphyrin moieties so that they can serve as vertices and/or edges and/or faces. In principle, the metal

Ultraselective Gas Separation by Nanoporous Metal−Organic Frameworks Embedded in Gas‐Barrier Nanocellulose Films

“…Materials : Zn(NO 3 ) was kindly provided by the Nippon Paper Co., Ltd. (Tokyo, Japan); the cellulose nanofi bers were produced from softwood Kraft pulp by TEMPO oxidation. [ 15 ] Synthesis of ZIF-90 : Zn(NO 3 ) 2 ·6H 2 O (0.743 g, 2.5 mmol) and ICA (0.961 g, 10 mmol) were added to DMF (25 mL), and the mixture was stirred at 80 °C for 4 h in an oil bath.…”

“…Metal-organic frameworks (MOFs) are nanoporous materials consisting of metal centers connected by various organic linkers, [ 3 ] which have uniform cavities and high surface areas effective for selective gas separation and have potential applications to catalysis, drug delivery, etc. [ 4 ] Recently, various polymer composite membranes containing MOFs, such as MOF-5 in Matrimid, [ 5 ] Cu-terephthalic acid in poly(vinyl alcohol), [ 6 ] and zeolitic imidazolate framework-90 (ZIF-90) in 2,2-bis(3,4-carboxyphenyl) hexafl uoropropane dianhydride-diaminomesitylene, [ 7 ] have occupied much attention in practical gas separation.…”

Directing two azo-bridged covalent metalloporphyrinic polymers as highly efficient catalysts for selective oxidation

“…Conversion (%) Yield (%) TOF This work 31 15 1.3 MMPF-3 [11] 96 58 69 PPF-1Co [11] 24 7 15 MMPF-5(Co) [12] 87 71 59 MMPF-5 [12] 9 5 4.2 Fe(TMP)Cl [33] Trace Trace 0 Au/TiO2 [34] 95 71 3.0 …”

“…Another strategy decorates the porphyrin macrocycle with bulky functional groups to protect the active sites, which is limited by the difficulty of synthesizing these porphyrins [6]. Currently, an additional strategy that has spurred tremendous interest is to incorporate or encapsulate heme into various networks, including metal metalloporphyrins-organic frameworks (MMOFs) [7][8][9][10][11][12][13], covalent metalloporphyrinic frameworks (CMFs) [14][15][16][17] and covalent metalloporphyrinic polymers (CMPs) [18][19][20][21][22]. Among them, covalent metalloporphyrinic polymers (CMPs) are the easiest to design and develop among the three aforementioned classes of materials, they are non-crystalline and have non-uniform pores that are typically somewhat ill-defined.…”

Synthesis, structures and physical properties of mixed-ligand coordination polymers based on a V-shaped dicarboxylic ligand

“…Coordination polymers (CPs) have gained immense attention not only because of their interesting structures and intriguing topologies, 1-3 but also their applications in diverse areas, such as gas storage and separation, 4-8 luminescence, [9][10][11][12] magnetism, 13,14 nonlinear optics, 15 catalysis, 16 proton conduction [17][18][19] etc.…”