Coherence in Metal鈭扢etal-to-Ligand-Charge-Transfer Excited States of a Dimetallic Complex Investigated by Ultrafast Transient Absorption Anisotropy

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• 作者：Sung Cho ; Michael W. Mara ; Xianghuai Wang ; Jenny V. Lockard ; Aaron A. Rachford ; Felix N. Castellano ; Lin X. Chen
• 刊名：Journal of Physical Chemistry A
• 出版年：2011
• 出版时间：April 28, 2011
• 年：2011
• 卷：115
• 期：16
• 页码：3990-3996
• 全文大小：913K
• 年卷期：v.115,no.16(April 28, 2011)
• ISSN：1520-5215

文摘

Coherence in the metal鈭抦etal-to-ligand-charge transfer (MMLCT) excited state of diplatinum molecule [Pt(ppy)(渭-^tBu₂pz)]₂ has been investigated through the observed oscillatory features and their corresponding frequencies as well as polarization dependence in the single-wavelength transient absorption (TA) anisotropy signals. Anticorrelated parallel and perpendicular TA signals with respect to the excitation polarization direction were captured, while minimal oscillatory features were observed in the magic angle TA signal. The combined analysis of the experimental results coupled with those previous calculated in the literature maps out a plausible excited state trajectory on the potential energy surface, suggesting that (1) the two energetically close MMLCT excited states due to the symmetry of the molecule may be electronically and coherently coupled with the charge density shifting back and forth between the two phenylpyridine (ppy) ligands, (2) the electronic coupling strength in the ¹MMLCT and ³MMLCT states may be extracted from the oscillation frequencies of the TA signals to be 160 and 55 cm^鈭?, respectively, (3) a stepwise intersystem crossing cascades follows ¹MMLCT 鈫?³MMLCT (T_1b) 鈫?³MMLCT (T_1a), and (4) a possible electronic coherence can be modulated via the Pt鈭扨t 蟽-interactions over a picosecond and survive the first step of intersystem crossing. Future experiments are in progress to further investigate the origin of the oscillatory features. These experimental observations may have general implications in design of multimetal center complexes for photoactivated reactions where coherence in the excited states may facilitate directional charge or energy transfer along a certain direction between different parts of a molecule.