Assembly of a trapped valent CeIII/IV–TCNQ complex through metal–ligand redox cooperativity

Himanshu Gupta; Brett D. Vincenzini; Alexandra M. Bacon; Eric J. Schelter

doi:10.1039/D4CC01478B

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Assembly of a trapped valent Ce^III/IV–TCNQ complex through metal–ligand redox cooperativity†

Himanshu Gupta,

^a Brett D. Vincenzini,^a Alexandra M. Bacon^a and Eric J. Schelter

*^a

Author affiliations

* Corresponding authors

^a P. Roy and Diana T. Vagelos Laboratories, Department of Chemistry, University of Pennsylvania, 231 South 34th Street, Philadelphia, Pennsylvania 19104, USA
E-mail: schelter@sas.upenn.edu

Abstract

Complex (Cp₃Ce^IV)₂(TCNQ)(Ce^IIICp₃)₂ (1) was prepared by reducing neutral TCNQ⁰ (tetracyanoquinodimethane) with Cp₃Ce(THF). Two types of cerium centres with a dianionic TCNQ²⁻ moiety are present in 1, wherein each of the four cyano-groups are bound by a cation. Formation of this trapped-valent organocerium compound 1 is facilitated by metal–ligand redox cooperativity. Characterization of 1 was carried out using structural-, magnetometry-, and IR-spectroscopic analyses. Photophysical studies on this compound reveal Ce^III luminescence, and opens up avenues for promising multifunctional, mixed-valent lanthanide materials.

This article is part of the themed collection: CC 60th Anniversary Authors Collection

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Article information

DOI: https://doi.org/10.1039/D4CC01478B
Article type: Communication
Submitted: 31 mar 2024
Accepted: 06 jun 2024
First published: 07 jun 2024
This article is Open Access

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Chem. Commun., 2024, Advance Article

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Assembly of a trapped valent Ce^III/IV–TCNQ complex through metal–ligand redox cooperativity

H. Gupta, B. D. Vincenzini, A. M. Bacon and E. J. Schelter, Chem. Commun., 2024, Advance Article , DOI: 10.1039/D4CC01478B

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