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http://dx.doi.org/10.5012/bkcs.2014.35.2.587

Unidirectional Photo-induced Charge Separation and Thermal Charge Recombination of Cofacially Aligned Donor-Acceptor System Probed by Ultrafast Visible-Pump/Mid-IR-Probe Spectroscopy  

Kim, Hyeong-Mook (Intelligent Textile System Research Center, Department of Chemistry, College of Natural Sciences, Seoul National University)
Park, Jaeheung (Department of Chemistry and Chemistry Institute of Functional Materials, Pusan National University)
Noh, Hee Chang (Department of Chemistry, Sangmyung University)
Lim, Manho (Department of Chemistry and Chemistry Institute of Functional Materials, Pusan National University)
Chung, Young Keun (Intelligent Textile System Research Center, Department of Chemistry, College of Natural Sciences, Seoul National University)
Kang, Youn K. (Department of Chemistry, Sangmyung University)
Publication Information
Bulletin of the Korean Chemical Society / v.35, no.2, 2014 , pp. 587-596 More about this Journal
Abstract
A new ${\pi}$-stacked donor-acceptor (D-A) system, [Ru(1-([2,2'-bipyridine]-6-yl-methyl)-3-(2-cyclohexa-2',5'-diene-1,4-dionyl)-1H-imidazole)(2,2':6',2"-terpyridine)]$[PF_6]_2$ (ImQ_T), has been synthesized and characterized. Similar to its precedent, [Ru(6-(2-cyclohexa-2',5'-diene-1,4-dione)-2,2':6',2"-terpyridine)(2,2':6',2"-terpyridine)]$[PF_6]_2$ (TQ_T), this system has a cofacial alignment of terpyridine (tpy) ligand and quinonyl (Q) group, which facilitates an electron transfer through ${\pi}$-stacked manifold. Despite the presence of lowest-energy charge transfer transition from the Ru-based-HOMO-to-Q-based-LUMO (MQCT) predicted by theoretical calculations by using time-dependent density functional theory (TD-DFT), the experimental steady-state absorption spectrum does not exhibit such a band. The selective excitation to the Ru-based occupied orbitals-to-tpy-based virtual orbital MLCT state was thus possible, from which charge separation (CS) reaction occurred. The photo-induced CS and thermal charge recombination (CR) reactions were probed by using ultrafast visible-pump/mid-IR-probe (TrIR) spectroscopic method. Analysis of decay kinetics of Q and $Q^-$ state CO stretching modes as well as aromatic C=C stretching mode of tpy ligand gave time constants of <1 ps for CS, 1-3 ps for CR, and 10-20 ps for vibrational cooling processes. The electron transfer pathway was revealed to be Ru-tpy-Q rather than Ru-bpy-imidazol-Q.
Keywords
Ru; NHC; Electron transfer; Charge separation; Time-resolved IR spectroscopy;
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