Metal–Organic Frameworks with Zero and Low–Valent Metal Nodes Connected by Tetratopic Phosphine Ligands

Sikma, R. Eric; Cohen, Seth M.

doi:10.1002/anie.202115454

Title: Metal–Organic Frameworks with Zero and Low–Valent Metal Nodes Connected by Tetratopic Phosphine Ligands

Journal Article · 05 January 2022 · Angewandte Chemie (International Edition)

DOI: https://doi.org/10.1002/anie.202115454 · OSTI ID:1871936

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Univ. of California, San Diego, La Jolla, CA (United States); U.C. San Diego
Univ. of California, San Diego, La Jolla, CA (United States)

Metal–organic frameworks (MOFs) constructed with M⁰ nodes are attractive targets due to the reactivity of these low-valent metals, but examples of these MOFs remain exceedingly rare. The rational design of three-dimensional MOFs with Pd⁰ and Pt⁰ nodes using tetratopic phosphine ligands is reported. Five new MOFs have been synthesized by systematic variation of the phosphine ligands and metal precursors employed, and these represent the first examples of MOFs constructed using phosphine–metal bonds as the sole structural component. Furthermore, the MOFs display solid-state luminescence, with emission maxima that are significantly red-shifted compared to Pd(PPh₃)₄. In addition, a Rh^I low-valent coordination solid based on the same linker design is reported, which displays solid-state luminescence that is not observed for the molecular analogue.

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Research Organization:: Univ. of California, San Diego, La Jolla, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division; National Science Foundation

Grant/Contract Number:: FG02-08ER46519

OSTI ID:: 1871936

Journal Information:: Angewandte Chemie (International Edition), Journal Name: Angewandte Chemie (International Edition) Journal Issue: 11 Vol. 61; ISSN 1433-7851

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

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