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Indexed by:期刊论文

Date of Publication:2008-02-01

Journal:JOURNAL OF THEORETICAL & COMPUTATIONAL CHEMISTRY

Included Journals:SCIE

Volume:7

Issue:1

Page Number:103-111

ISSN No.:0219-6336

Key Words:ligand-to-ligand charge transfer; intraligand charge transfer; metal-to-ligand charge transfer; sequential protonations; theory of molecular orbital transitions

Abstract:Visualized theoretical evidence for successively switching from ligand-to-ligand charge transfer (LLCT) to intraligand charge transfer (ILCT) and then to metal-to-ligand charge transfer (MLCT) excited states in platinum(II) terpyridyl acetylide (PTA) complexes in low-energy absorption by sequential protonations has been given with charge transfer density, based on recently experimental report (Han X. et al., Chem Eur J 13: 1231, 2007). The sequential protonations have shown significant influence on the molecular geometries, ionization potential, affinity potential, and band gap of PTA. The protonations on the amino group of the ligands result in the shift of the molecular orbital energy levels of PTA. The physical mechanism of switching from LLCT to ILCT and then to MLCT excited states by sequential protonations is interpreted with the theory of molecular orbital transitions.