Theoretical study on photophysical properties of angular-shaped mercury(II) bis(acetylide) complexes as light-emitting materials

• Published in: Chemical physics 2010-02, Vol.368 (1), p.66-75
• Main Authors: Ran, Xue-Qin, Feng, Ji-Kang, Wong, Wai-Yeung, Ren, Ai-Min, Poon, Suk-Yue, Sun, Chia-Chung
• Format: Article
• Language: English
• Subjects: LMCT; Mercury-containing arylacetylenes; Optoelectronic properties; TD-DFT
• ISSN: 0301-0104
• DOI: 10.1016/j.chemphys.2009.12.019

An in-depth investigation on the optical and electronic properties of a series of mercury-containing and metal-free arylacetylenes with bridged heteroatoms was provided here. The geometric and electronic structures of the complexes in the ground state are studied with density functional theory and Hartree–Fock, whereas the lowest singlet and triplet excited states are optimized by singles configuration interaction (CIS) methods. At the time-dependent density functional theory (TD-DFT) level, molecular absorptions and emission properties were calculated on the basis of optimized ground- and excited-state geometries, respectively. The calculated lowest-lying absorptions of the investigated complexes are attributed to ligand-to-ligand charge transfer (LLCT), intraligand (IL) and ligand-to-metal charge transfer (LMCT). The results show that the optoelectronic properties for the complexes are affected by the transition-metal atom, various bridge heteroatoms and different end-group substituents. Moreover, the calculated data reveal that the studied molecules have improved charge-transfer rate, especially for designed molecules.