Theoretical Study on the Electronic Structure and Optical Properties of Mercury-Containing Diethynylfluorene Monomer, Oligomer, and Polymer

Abstract

We present a first-principles study of the structural, electronic, and optical properties on mercury-containing diethynylfluorene monomer, oligomer, and polymer. The aim of our quantum-chemical calculations is to shed light on the role of the transition metal centers in the organometallic system in terms of electronic structure and to estimate the influence of metal on the optical properties of the mercury polyyne polymer as well as the nature of luminescence in the polymer. The results indicate that there is a weak electronic interaction between the metal-based fragment and the π-conjugated organic segments, and consequently the photophysical properties are mainly based on the diethynylfluorene π-conjugated fragment (TFT) with little contribution from the metal center. The role of the metal center can be described as weak delocalization coupled with strong localization characteristics along the organometallic polymer backbone. The lowest singlet and triplet excited state have been studied by the singles ...