Electron/Energy Transfer Studies on Hybrid Materials Based on Dinuclear Coordination Compounds of Twisted Perylene Diimide

摘要： To understand the influence of transition metal ion coordination on the properties and performance of the triads, the symmetric bridging ligand, 1,10-phenanthroline-perylene diimide-1,10-phenanthroline, 1,10-Phen-PDI-1,10-Phen (1) comprising four electron-donating 4-methoxyphenoxy bulky groups at bay-positions and its corresponding square-planar coordination compounds with dichloroplatinum(II), [{PtCl2}2-1] (2) and palladium(II) [{PdCl2}2-1] (3) were prepared in order to tune the photochemical and optical properties of these hybrid materials. These triads show strong electronic absorption bands attributed to the PDI and M(II)(1,10-Phen)Cl2 moieties in DMSO. UV-Vis absorption spectra of compounds were calculated using Time-Dependent Density Functional Theory (TDDFT) for the ground state optimized structures in DCM. Current results indicate that 2 has the lowest HOMO-LUMO gap (2.29 eV in DCM) among the investigated molecules. The energy and charge transfer processes with tailoring molecular structures are one of the important strategies for the design of future functional triads based on donor and acceptor moieties for hybrids optoelectronic devices. Thus, we studied linear absorption, fluorescence, and ultrafast transient absorption spectra measurements for the triads in dichloromethane to investigate the impact of different functionalization strategies on the optical characteristics, photo-stability, and photo-induced charge-transfer (CT) processes. The observed ultrafast intramolecular charge transfer from donor units to acceptor part of 1, 2 and 3 is related to fluorescence quenching and faster singlet state decay on transient absorption measurements. The intramolecular charge transfer mechanism was also compared with the unsymmetrical counterparts that were investigated previously. Symmetrical compounds exhibit faster charge transfer in comparison with the unsymmetrical compounds.