A porous coordination polymer (PCP) has been synthesized employing an organic ligand in which a stable free radical, isoindoline nitroxide, is incorporated. The crystalline PCP possesses one-dimensional channels decorated with the nitroxyl catalytic sites. When O2 gas or air was used as the oxidant, this PCP was verified to be an efficient, recyclable, and widely applicable catalyst for selective oxidation of various alcohols to the corresponding aldehydes or ketones.
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http://dx.doi.org/10.1021/ja5019095 | DOI Listing |
ACS Nano
January 2025
Creative Research Initiative Center for Nanospace-confined Chemical Reactions (NCCR), Pohang University of Science and Technology (POSTECH), Pohang 37673, Korea.
Unlike homogeneous metal complexes, achieving absolute control over reaction selectivity in heterogeneous catalysts remains a formidable challenge due to the unguided molecular adsorption/desorption on metal-surface sites. Conventional organic surface modifiers or ligands and rigid inorganic and metal-organic porous shells are not fully effective. Here, we introduce the concept of "ligand-porous shell cooperativity" to desirably reaction selectivity in heterogeneous catalysis.
View Article and Find Full Text PDFNanoscale
January 2025
Department of Chemistry, Indian Institute of Technology Patna, Patna 801106, Bihar, India.
Covalent organic frameworks (COFs) are crystalline porous materials bearing well-ordered two- or three-dimensional molecular tectons in their polymeric skeletal framework. COFs are structurally robust as well as physiochemically stable. Currently, these are being developed for their use as "heterogeneous catalysts" for various organic transformations.
View Article and Find Full Text PDFAdv Mater
January 2025
State Key Laboratory of Coordination Chemistry, Key Laboratory of Mesoscopic Chemistry of MOE, Jiangsu Key Laboratory of Advanced Organic Materials, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, 210023, P. R. China.
Porous liquids (PLs) have emerged as a promising class of flow porous materials, offering distinctive benefits for sustainable separation processes coupled with catalytic transformations in the chemical industry. Despite their potential, challenges remain in the realms of synthesis complexity, stability, and the strategic engineering of separation and catalytic sites. In this study, a scalable mechanochemical synthetic approach is reported to fabricate Type III PLs from solid precursors with high stability.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
January 2025
Xi'an Jiaotong University, School of Chemical Engineering and Technology, CHINA.
We report herein two families of porous coordination clusters (PCCs) with 216 nuclearity (M120RE96 or PCC-216MR) and 300 nuclearity (Co144Gd156 or PCC-300CG). For the first family M could be either nickel or cobalt, and RE = Pr, Nd, Sm, Eu, and Gd; while the latter features the highest nuclearity of transition-rare earth metal clusters. Characterized by their cube-like, hollow structures, these clusters exhibit the ability to absorb N2 and CO2.
View Article and Find Full Text PDFJ Am Chem Soc
January 2025
Department of Chemistry, Tsinghua University, Beijing 100084, P. R. China.
Coordinatively unsaturated copper (Cu) has been demonstrated to be effective for electrifying CO reduction into C products by adjusting the coupling of C-C intermediates. Nevertheless, the intuitive impacts of ultralow coordination Cu sites on C products are scarcely elucidated due to the lack of synthetic recipes for Cu with low coordination numbers and its vulnerability to aggregation under reductive potentials. Herein, computational predictions revealed that Cu sites with higher levels of coordinative unsaturation favored the adsorption of C and C intermediates.
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