Theoretical insights into the effect of amine and phosphine decoration on the photoluminescence of copper(i) and silver(i) coordination polymers

Abstract

Coinage metal cyanides (MCN) form photoluminescent 1D coordination polymers. The decoration of these chains with amine and phosphine ligands shifts the wavelength for photoluminescence into the visible region. Density-functional theory (DFT) and time-dependent DFT (TD-DFT) calculations of zigzag and helical models of decorated chains are used to show that the transitions that contribute to the experimental spectra are related to the π-π excitations previously shown for coinage metal cyanide chains.

Halocuprate(i) zigzag chain structures with N-methylated DABCO cations – bright metal-centered luminescence and thermally activated color shifts

“…In this rather crude model, the periodicity of the system is neglected. 48 ((Insert Figure 5 here)) Moreover, the emission decay time of compound 1 was also investigated in dependence of temperature, see Figure 7. In one type, the central copper and bromide atoms are arranged in a butterfly like shape (butterfly type, A) whereas in the other segment type these atoms are located in one plane (planar type, B).…”

“…It is mentioned that in a recent report, a similar situation was described for a copper cyanide chain where the occurrence of different emission energies was also attributed to the existence of different chain segments. 48 Moreover, the emission decay time of compound 1 was also investigated in dependence of the temperature, see Fig. 7.…”

“…[28][29][30][31][32][33][34][35][36][37][38][39][40][41][42]72,73 Although many studies have been performed during recent years on the emission behavior of Cu(I) complexes due to their potential for use as low-cost emitter materials for OLEDs, [36][37][38][39][40][41][42][43][44][45][68][69][70][71][72] only very limited investigations in this regard were carried out on copper-halide chains, such as the ones presented in this contribution. [46][47][48]73,[75][76][77] Herein, the syntheses, crystal structures, and photophysical properties of two new luminescent halocuprate(I) compounds containing chains of trans edge-sharing tetrahedra are presented and discussed. This structure type is connected with the occurrence of specific chain segments which largely determine the emission behavior as is elucidated, in particular, for compound 1.…”