Electroreduction-Driven Formation and Connectivity of Polyoxometalate Coordination Networks

Chang, Haeun [University of California, San Diego, La Jolla, CA (United States)]; Chen, Linfeng [University of California, San Diego, La Jolla, CA (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)] (ORCID:0000000204363197); Samolova, Erika [University of California, San Diego, La Jolla, CA (United States); Institute of Physics of the Czech Academy of Sciences (Czech Republic)]; Pan, Yuanhui [University of California, San Diego, La Jolla, CA (United States)] (ORCID:0000000223046314); Acosta, Kody A. [University of California, San Diego, La Jolla, CA (United States)]; Lemmon, Carl E. [University of California, San Diego, La Jolla, CA (United States)]; Gembicky, Milan [University of California, San Diego, La Jolla, CA (United States)] (ORCID:0000000238981612); Paesani, Francesco [University of California, San Diego, La Jolla, CA (United States)] (ORCID:0000000244511203); Schimpf, Alina M. [University of California, San Diego, La Jolla, CA (United States)] (ORCID:0000000154027426)

doi:10.1021/acs.inorgchem.4c04891

DOE OSTI · 2502120

Electroreduction-Driven Formation and Connectivity of Polyoxometalate Coordination Networks

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Abstract

We present the synthesis of metal oxide coordination networks based on Preyssler-type polyoxoanions ([NaP 5 W 30 O 110 ] 14– and [NaP 5 MoW 29 O 110 ] 14– ) bridged with metal–aquo complexes ([M(H 2 O) n ] m+ , M m+ = Co 2+ , Ni 2+ , Zn 2+ , Y 3+ ), induced by electrochemical reduction. Networks bridged with first-row transition metals are isostructural with a previously reported Co-bridged structure, while the Y 3+ -bridged structure is new. All networks feature an uncommon binding motif of the metal cation to the oxygen atoms at cap positions, which we hypothesize is due to increased electron density at the cap upon reduction. Oxidation of a Zn 2+ -bridged network resulted in a new structure in which Zn 2+ –O cap bonds are lost, indicating the importance of reduction in the connectivity of these polyoxometalate-based coordination networks.

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY Chemical structure Crystal structure Electrochemical reduction Electrodes Oxidation

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Chang, Haeun [University of California, San Diego, La Jolla, CA (United States)], Chen, Linfeng [University of California, San Diego, La Jolla, CA (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)] (ORCID:0000000204363197), Samolova, Erika [University of California, San Diego, La Jolla, CA (United States); Institute of Physics of the Czech Academy of Sciences (Czech Republic)], Pan, Yuanhui [University of California, San Diego, La Jolla, CA (United States)] (ORCID:0000000223046314), Acosta, Kody A. [University of California, San Diego, La Jolla, CA (United States)], Lemmon, Carl E. [University of California, San Diego, La Jolla, CA (United States)], Gembicky, Milan [University of California, San Diego, La Jolla, CA (United States)] (ORCID:0000000238981612), Paesani, Francesco [University of California, San Diego, La Jolla, CA (United States)] (ORCID:0000000244511203), Schimpf, Alina M. [University of California, San Diego, La Jolla, CA (United States)] (ORCID:0000000154027426). 2025-01-16. Electroreduction-Driven Formation and Connectivity of Polyoxometalate Coordination Networks. https://doi.org/10.1021/acs.inorgchem.4c04891

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