A FIRST PRINCIPLE ANALYSIS ON THE STRUCTURAL AND PHOTO-INDUCED CHARGE TRANSFER IN RUTHENIUM COMPLEXES OF HEXAAZATRIPHENYLENE

作者：Liu Sha Sha; Liu Xiao Xia^*; Qiu Kang; Song Peng

来源：Journal of Theoretical and Computational Chemistry, 2012, 11(4): 895-905.

DOI：10.1142/S0219633612500605

• Ruthenium complexes of hexaazatriphenylene
• metal-to-ligand charge transfer
• density functional theory
• long range corrected functional CAM-B3LYP

Three complexes [Ru(CN)(4)(HAT)](2) (HAT = hexaazatriphenylene; [Ru-1](2-)), [Ru(CN)(4)}(2) (mu(2)- HAT)](4-)([Ru-2](4-)) and [{Ru(CN)(4)}(3)(mu(3)-HAT)](6-)([Ru-3](6-)) for supramolecular assemblies are investigated by quantum-chemical calculations. Due to symmetry of complexes, the energy level differences are 2.014 eV and 2.019 eV for [Ru-2](4-) and [Ru-3](6-) complex, which are about 0.4 eV larger than that for [Ru-1](2-) complex. The absorption maximum for [Ru-1](2-) complex in water is at 375.8 nm. Coordination of the second and third Ru(II) center to produce [Ru-2](4-) and [Ru-3](6-) result in a red-shift of this strongest absorption to 453.4 nm and 468.1 nm, respectively. Absorption maximum of three complexes belong to MLCT transitions, which are revealed by frontier molecular orbital theory and charge difference density method.

• 出版日期2012-8
• 单位东北大学; 辽宁大学