화학공학소재연구정보센터
Journal of Physical Chemistry A, Vol.119, No.27, 7026-7037, 2015
Theoretical Rationalization of the Emission Properties of Prototypical Cu(I)-Phenanthroline Complexes
The excited state properties of transition metal complexes have become a central focus of research owing to a wide range of possible applications that seek to exploit their luminescence properties. Herein, we use density functional theory (DFT), time-dependent DFT (TDDFT), classical and quantum mechanics/molecular mechanics (QM/MM) molecular dynamics (MD) simulations to provide a full understanding on the role of the geometric and electronic structure, spin orbit coupling, singlet triplet gap and the solvent environment on the emission properties of nine prototypical copper(I)-phenanthroline complexes. Our calculations reveal clear trends in the electronic properties that are strongly correlated to the luminescence properties, allowing us to rationalize the role of specific structural modifications. The MD simulations show, in agreement with recent experimental observations, that the lifetime shortening of the excited triplet state in donor solvents (acetonitrile) is not due to the formation of an exciplex. Instead, the solute solvent interaction is transient and arises from solvent structures that are similar to the ones already present in the ground state. These results based on a subset of the prototypical mononuclear Cu(I) complexes shed general insight into these complexes that may be exploited for development of mononuclear Cu(I) complexes for applications as, for example, emitters in third generation OLEDs.