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

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

Chem Commun (Camb). 2024 Jul 2;60(54):6909-6912. doi: 10.1039/d4cc01478b.

Authors

Himanshu Gupta¹, Brett D Vincenzini¹, Alexandra M Bacon¹, Eric J Schelter¹

Affiliation

¹ P. Roy and Diana T. Vagelos Laboratories, Department of Chemistry, University of Pennsylvania, 231 South 34th Street, Philadelphia, Pennsylvania 19104, USA. [email protected].

PMID: 38881335
DOI: 10.1039/d4cc01478b

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 TCNQ^2- 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.