Gong Z.-JNarayana Y.S.L.VLin Y.-CHuang W.-HSu W.-NYI-PEI LIHiguchi MWen-Yueh Yu2022-11-162022-11-16202209263373https://www.scopus.com/inward/record.uri?eid=2-s2.0-85128425112&doi=10.1016%2fj.apcatb.2022.121383&partnerID=40&md5=6c265bb1d7c5424833675971a807181ahttps://scholars.lib.ntu.edu.tw/handle/123456789/625128Ruthenium-based metallo-supramolecular polymers (Ru-MSPs) were synthesized by complexing Ru ions with 1,4-bis(1,10-phenanthrolin-5-yl)benzene ligands for heterogeneously catalytic transfer hydrogenation of carbonyl compounds with formate. The degree of polymerization and the local environment of Ru atoms in Ru-MSP were tailored by tuning the ligand/metal ratio and the synthesis temperature/period. The coordinatively-unsaturated Ru atoms are identified as the active centers in Ru-MSP for carbonyl reduction. Ru-MSP is much more active than Ru-based counterparts including its monomeric analogue, which is attributed to (1) the higher electron density in Ru atoms that facilitates the selective dehydrogenation of formate via C-H dissociation, and (2) the lower LUMO of ligand moieties that activates the carbonyl oxygen via Lewis acid-base interactions. Furthermore, Ru-MSP displays high reusability and capability of catalyzing a wide scope of carbonyl compounds. These findings demonstrate that the rationally-designed polymerization is a promising approach to heterogenize the catalytically active metal complexes with enhanced performance. © 2022 Elsevier B.V.Carbonyl reduction; Catalytic transfer hydrogenation; Heterogeneous catalyst; Metallo-supramolecular polymerAtoms; Carbonyl compounds; Carbonylation; Catalysts; Chelation; Hydrogenation; Metal complexes; Metals; Polymerization; Reusability; Supramolecular chemistry; Carbonyl reduction; Catalytic transfer hydrogenation; Degrees of polymerizations; Heterogeneous catalyst; Local environments; Metallo-supramolecular; Metallo-supramolecular polymer; Rational synthesis; Supramolecular polymers; Synthesised; LigandsRational synthesis of ruthenium-based metallo-supramolecular polymers as heterogeneous catalysts for catalytic transfer hydrogenation of carbonyl compoundsjournal article10.1016/j.apcatb.2022.1213832-s2.0-85128425112