When do tripdoublet states fluoresce? A theoretical study of copper(II) porphyrin

Abstract

Open-shell molecules rarely fluoresce, due to their typically faster non-radiative relaxation rates compared to closed-shell ones. Even rarer is the fluorescence from states that have two more unpaired electrons than the open-shell ground state, for example tripdoublet states (a triplet excitation antiferromagnetically coupled to a doublet state). The description of the latter states by U-TDDFT is notoriously inaccurate due to large spin contamination. In this work, we applied our spin-adapted TDDFT method, X-TDDFT, and the static-dynamic-static second order perturbation theory (SDSPT2), to the study of the excited states as well as their relaxation pathways of copper(II) porphyrin; previous experimental works suggested that the photoluminescence of some substituted copper(II) porphyrins originate from a tripdoublet state, formed by a triplet ligand $\pi\to\pi^*$ excitation. Our results demonstrated favorable agreement between the X-TDDFT, SDSPT2 and experimental excitation energies, and revealed noticeable improvements of X-TDDFT compared to U-TDDFT, suggesting that X-TDDFT is a reliable tool for the study of tripdoublet fluorescence. Intriguingly, the aforementioned tripdoublet state is the lowest doublet excited state and lies only slightly higher than the lowest quartet state, which explains why the tripdoublet of copper(II) porphyrin is long-lived enough to fluoresce; an explanation for this unusual state ordering is given. Indeed, thermal vibration correlation function (TVCF)-based calculations of internal conversion, intersystem crossing, and radiative transition rates confirm that copper(II) porphyrin emits thermally activated delayed fluorescence (TADF) and a small amount of phosphorescence at low temperature (83 K), in accordance with experiment. The present contribution is concluded by a few possible approaches of designing new molecules that fluoresce from tripdoublet states.