Superstructures of Copper Nanoclusters as NIR TADF Emitters: Solvent-dependent Optical and Morphological Modulation

Abstract

Herein, we report 2-mercaptopyridine-templated copper nanoclusters (CuNCs) which display near infra-red (NIR) emission, both in the solid and colloidal states. Interestingly, the NIR emission can be modulated to orange emission by preparing the CuNCs in a mixed solvent system of chloroform and methanol instead of water. The drastic change in the photo-physical properties of CuNCs when prepared in two different solvent systems is accompanied by a unique morphological tuning. Further studies reveal that the strong NIR emission is the result of thermally activated delayed fluorescence (TADF) which is confirmed by long excited state lifetime (~4 µs in room temperature), Time Resolved Emission Spectroscopy (TRES) measurements, temperature-dependent photoluminescence studies, temperature-dependent lifetime studies, and excitation-transmittance dependent TRES intensity measurements. The CuNCs exhibit an exceptionally small singlet-triplet energy gap of 58.2 meV, indicating a highly efficient TADF in the system. Moreover, the solvent-dependent morphological tuning of the nanocluster superstructures rendering drastic change in the photo-physical signatures is the consequence of different ΔE(S1-T1) values for the CuNCs in different solvent environments. Further findings corroborate that the electronic structure of the surface ligands can also help us to tune the ΔE(S1-T1) energy gap for these nanoclusters.