Metal-organic layers as multifunctional two-dimensional nanomaterials for enhanced photoredox catalysis

Article abstract of DOI:10.1021/jacs.9b08956

Metal-organic layers (MOLs) have recently emerged as a novel class of molecular two-dimensional (2D) materials with significant potential for catalytic applications. Herein we report the design of a new multifunctional MOL, Hf₁₂-Ir-Ni, by laterally linking Hf₁₂ secondary building units (SBUs) with photosensitizing Ir(DBB)[dF(CF₃)ppy]₂⁺ [DBB-Ir-F, DBB = 4,4′-di(4-benzoato)-2,2′-bipyridine; dF(CF₃)ppy = 2-(2,4-difluorophenyl)-5-(trifluoromethyl)pyridine] bridging ligands and vertically terminating the SBUs with catalytic Ni(MBA)Cl₂ [MBA = 2-(4′-methyl-[2,2′-bipyridin]-4-yl)acetate] capping agents. Hf₁₂-Ir-Ni was synthesized in a bottom-up approach and characterized by TEM, AFM, PXRD, TGA, NMR, ICP-MS, UV-vis, and luminescence spectroscopy. The proximity between photosensitizing Ir centers and catalytic Ni centers (～0.85 nm) in Hf₁₂-Ir-Ni facilitates single electron transfer, leading to a 15-fold increase in photoredox reactivity. Hf₁₂-Ir-Ni was highly effective in catalytic C-S, C-O, and C-C cross-coupling reactions with broad substrate scopes and turnover numbers of ～4500, ～1900, and ～450, respectively.

Full text of DOI:10.1021/jacs.9b08956

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Communication
Metal-Organic Layers as Multifunctional 2D
Nanomaterials for Enhanced Photoredox Catalysis
Guangxu Lan, Yangjian Quan, Maolin Wang, Geoffrey T Nash, Eric
You, Yang Song, Samuel S. Veroneau, Xiaomin Jiang, and Wenbin Lin
J. Am. Chem. Soc., Just Accepted Manuscript • DOI: 10.1021/jacs.9b08956 • Publication Date (Web): 24 Sep 2019
Downloaded from pubs.acs.org on September 25, 2019
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ACS Paragon Plus Environment

Journal of the American Chemical Society
Page 6 of 6
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ACS Paragon Plus Environment