Role of Spin-Orbit Coupling in Long Range Energy Transfer in Metal-Organic Frameworks.

Abstract

Metal-organic frameworks (MOFs) are emerging as a promising platform for solar energy conversion applications. Their potential utilization as efficient chromophores in artificial photosynthesis is closely related to the understanding of light-harvesting and energy transfer processes that occur within these molecular scaffolds. Herein, we present the photophysical investigation of Ru(II), Ir(III), and Os(II) polypyridyl complexes incorporated into the backbone of UiO-67. In this work, we systematically study the effect of spin-orbit coupling on dipole-dipole energy transfer in MOFs using steady-state and time-resolved spectroscopic techniques. The results of our work indicate successful triplet-to-singlet energy transfer and a sizable increase in the transfer kinetics and critical distance, as direct consequences of strong spin-orbit couplings. Remarkably, the reported R0 value for OsDCBPY (R0 = 88 ± 10 Å) represents one of the largest Förster distances observed in an MOF. Collectively, this work contributes to the general knowledge of energy transfer in materials and provides groundwork for efficient utilization in artificial photosynthetic assemblies.