Temperature-Dependent Spin-Driven Dimerization Determines the Ultrafast Dynamics of a Copper(II)-Bound Tripyrrindione Radical

Anshu Kumar, Benjamin Thompson, Ritika Gautam, Elisa Tomat, Vanessa Huxter

Research output: Contribution to journalArticlepeer-review

1 Scopus citations

Abstract

Radicals and other open-shell molecules play a central role in chemical transformations and redox chemistry. While radicals are often highly reactive, stable radical systems are desirable for a range of potential applications, ranging from materials chemistry and catalysis to spintronics and quantum information. Here we investigate the ultrafast properties of a stable radical system with temperature-dependent spin-tunable properties. This radical complex, Cu(II) hexaethyl tripyrrin-1,14-dione, accommodates unpaired electrons localized on both the copper metal center and the tripyrrolic ligand. The unusual combination of two unpaired electrons and high stability in this radical molecule enable switchable temperature-dependent spin coupling. Two-dimensional electronic spectroscopy measurements of Cu(II) hexaethyl tripyrrin-1,14-dione were collected at room temperature and at 77 K. At room temperature, the molecules are present as monomers and have short picosecond lifetimes. At 77 K, the molecules are present in a dimer form mediated by ferromagnetic and antiferromagnetic coupling. This reversible spin-driven dimerization changes the optical properties of the system, generating long-lived excitonic states.

Original languageEnglish (US)
Pages (from-to)11268-11273
Number of pages6
JournalJournal of Physical Chemistry Letters
Volume14
Issue number50
DOIs
StatePublished - Dec 21 2023

ASJC Scopus subject areas

  • General Materials Science
  • Physical and Theoretical Chemistry

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