Construction of Ultrastable Porphyrin Zr Metal–Organic Frameworks through Linker Elimination

Abstract

A series of highly stable MOFs with 3-D nanochannels, namely PCN-224 (no metal, Ni, Co, Fe), have been assembled with six-connected Zr6 cluster and metalloporphyrins by a linker-elimination strategy. The PCN-224 series not only exhibits the highest BET surface area (2600 m(2)/g) among all the reported porphyrinic MOFs but also remains intact in pH = 0 to pH = 11 aqueous solution. Remarkably, PCN-224(Co) exhibits high catalytic activity for the CO2/propylene oxide coupling reaction and can be used as a recoverable heterogeneous catalyst.

Cycloadditions to Epoxides Catalyzed by Group III–V Transition‐Metal Complexes

“…[57],c opyright 2014 the American Chemical Society; Right)PCN-224 (reproduced with permission from Ref. [59],copyright 2013 the American Chemical Society). 7,1906 -1917 www.chemcatchem.org to selected epoxides (PO, styrene oxide,d ivinylbenzened ioxide) and CO 2 under ambient conditions.…”

Assembly of Covalently Inorganic-Organic Hybrid Molecular Framework Based on Porphyrin and Phthalocyanine Derivatives—Sensitizer for Dye Sensitized Solar Cells

“…The similar film of carboxyphenyl porphyrin Co complex-Al-O cluster supplied the same catalytic behavior [26]. Different MOFs based on tetra(4-carboxyphenyl)porphyrin Fe complex-Zr-O cluster can also be selected as catalyst in catalytic conversion from CO 2 to ethylene glycol lactone [27] [33]. Another MOFs of tetra(4-carboxyphenyl)porphyrin Sn complex-W-O cluster possessed multifunctional activity in catalysis [34].…”

“…Recently, a specialized commentary about heterogeneous catalysis was reviewed [36]. Assembly types of MOFs based on porphyrin/phthalocyanine were summarized as: 1) porphyrin molecules (peripheral groups were usually selected as carboxyl) were combined with hard acid-O clusters, and the hard acids were high valence ions, including Al and Zr [25] [26] [27] [28]; 2) porphyrin molecules were linked with complexes (i.e., Ni-pyridine complexes) [29]; 3) peripheral-central axial coordination and bridge axial coordination constructed crystal porphyrin MOFs; and 4) covalent bond bridged porphyrins mainly depended on covalently conjugate pair of Schiff base bonds, which were constructed by the condensation between aminophenyl porphyrins with p-phthalaldehyde and with biphenyl-4, 4'-dicarboxaldehyde. These MOFs were also known as COFs (Covalent Organic Frameworks) [11] [30]- [38].…”

Heterogeneous catalytic properties of unprecedented μ-O-[FeTCPP]2dimers (H2TCPP = meso-tetra(4-carboxyphenyl)porphyrin): an unusual superhyperfine EPR structure

“…35,36 Thus, our proposal is using the catalyst as a structural unit. As concluded by several recent works, [37][38][39][40][41][42][43][44][45][46][47][48][49] this approach has been observed to be effective. However, the number of metalloporphyrinic compounds in which the network itself 60 plays as a catalyst is very low.…”