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

Sikma, R. Eric; Cohen, Seth M.

doi:10.1002/ange.202115454

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

Journal Article · Wed Jan 26 23:00:00 EST 2022 · Angewandte Chemie

DOI:https://doi.org/10.1002/ange.202115454· OSTI ID:1842540

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Department of Chemistry and Biochemistry University of California San Diego, La Jolla CA 92093 USA

Abstract

Metal–organic frameworks (MOFs) constructed with M ⁰ 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 Pd ⁰ and Pt ⁰ 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. The MOFs display solid‐state luminescence, with emission maxima that are significantly red‐shifted compared to Pd(PPh ₃ ) 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.

View Accepted Manuscript (Publisher)

Sponsoring Organization:: USDOE

Grant/Contract Number:: NONE; FG02-08ER46519

OSTI ID:: 1842540

Journal Information:: Angewandte Chemie, Journal Name: Angewandte Chemie Journal Issue: 11 Vol. 134; ISSN 0044-8249

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

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

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