Fully meta‐Substituted 4, 4′‐Biphenyldicarboxylate‐Based Metal–Organic Frameworks: Synthesis, Structures, and Catalytic Activities. Issue 11 (21st March 2017)

• Record Type: Journal Article
• Authors: Li, Jiawei; Ren, Yanwei; Qi, Chaorong; Jiang, Huanfeng
• Is Part Of: European journal of inorganic chemistry. Issue 11(2017)
• Page Start: 1478
• Page End: 1487
• Publication Date: 2017-03-21
• Subjects: Metal–organic frameworks -- Heterogeneous catalysis -- Cyanosilylation -- Epoxidation -- Carbon dioxide fixation; Chemistry, Inorganic -- Periodicals; Organometallic chemistry -- Periodicals; Bioinorganic chemistry -- Periodicals; Solid state chemistry -- Periodicals; 546
• DOI: 10.1002/ejic.201601242
• Languages: English
• ISSNs: 1434-1948

Abstract

Abstract : Fully meta ‐substituted 2, 2′, 6, 6′‐tetramethoxy‐4, 4′‐biphenyldicarboxylic acid (H2 L) was synthesized and applied in the construction of three metal–organic frameworks (MOFs), {[Cu3 L3 (H2 O)2 (DMF)] n (1 ), [Zn4 OL3 ] n (2 ), and [Zn4 OL3 (H2 O)(DEF)] n (3 )}. For1, the approximately vertical twist of two benzene rings in L leads to the formation of a twofold‐interpenetrated 3D structure with 1D open channels (11 × 15 Å). MOFs2 and3 have classical twofold‐interpenetrated isoreticular MOF structures, and reversible transformation of the oxozinc carboxylate clusters of2 and3 could be realized via a solvent‐exchange‐induced single‐crystal‐to‐single‐crystal pathway, which provides direct structural evidence for a Zn4 O core as Lewis acidic site in MOFs. Desolvated framework1′ exhibits high permanent porosity (Langmuir surface area = 555 m 2 /g), high thermal stability (up to 300 °C), and highly active catalytic properties for cyanosilylation and olefin epoxidation. MOF2 exhibits moderate carbon dioxide uptake ability and can efficiently catalyze the cycloaddition of CO2 with epoxides under mild conditions. Abstract : A three‐dimensional Cu‐MOF (MOF = metal–organic framework) based on 2, 2′, 6, 6′‐tetramethoxy‐4, 4′‐biphenyldicarboxylic acid exhibits high catalytic activities for cyanosilylation and olefin epoxidation reactions. A Zn‐MOF based on the same ligand shows excellent catalytic activity for the synthesis of cyclic carbonates from epoxides and CO2 under mild conditions.