Effects of the reaction cavity on metastable optical excitation in ruthenium-sulfur dioxide complexes

TL;DR

This study investigates how the local crystal environment affects metastable optical excitation in ruthenium-sulfur dioxide complexes, revealing the influence of reaction cavity on excited-state geometries and photoconversion efficiency.

Contribution

It demonstrates that the local crystal environment significantly influences the excited-state geometries and photoconversion fractions in ruthenium-sulfur dioxide complexes, advancing understanding for optical data-storage design.

Findings

Metastable excited states observed at 100 K with specific photoconversion fractions.

Solid-state DFT calculations show local environment impacts excited-state geometries.

Different ligand environments lead to varying photoconversion efficiencies.

Abstract

We report photoexcited-state crystal structures for two new members of the [Ru(SO_2)(NH_3)_4X]Y family: 1:X=H2O, Y=(+/-)-camphorsulfonate_2; 2:X=isonicotinamide, Y=tosylate_2. The excited states are metastable at 100 K, with a photoconversion fraction of 11.1(7)% achieved in 1, and 22.1(10)% and 26.9(10)% at the two distinct sites in 2.We further show using solid-state density-functional-theory calculations that the excited-state geometries achieved are strongly influenced by the local crystal environment. This result is relevant to attempts to rationally design related photoexcitation systems for optical data-storage applications.