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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Ultrafast Dynamics in the Metal-to-Ligand Charge Transfer Excited-State Evolution of [Ru(4,4'-diphenyl-2,2'-bipyridine)_3]~(2+)
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Ultrafast Dynamics in the Metal-to-Ligand Charge Transfer Excited-State Evolution of [Ru(4,4'-diphenyl-2,2'-bipyridine)_3]~(2+)

机译：[Ru（4,4'-diphenyl-2,2'-bipyridine）_3]〜（2+）的金属到配体电荷转移激发态演化的超快动力学

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摘要

The transition metal complexes [Ru(dmb)_3]~(2+) and [Ru(dpb)_3]~(2+), where dmb is 4,4'-dimethyl-2,2'-bipyridine and dpb is 4,4'-diphenyl-2,2'-bipyridine, have been studied by femtosecond visible electronic absorption spectroscopy. Spectroelectrochemical measurements in conjunction with nanosecond time-resolved absorption spectroscopy allow for the assignment of various features in the excited-state differential absorption spectra as both ligand-based #pi#~* implied by #pi#~* and ligand-to-metal charge transfer (LMCT) in nature. A unique absorptive feature centered at approx 530 nm in [Ru(dpb)_3]~(2+) was identified as an optical marker for the thermalized (and hence fully intraligand delocalized) excited state. Single wavelength and full spectrum transient absorption data were obtained on both molecules in CH_3CN solution at room temperature following metal-to-ligand charge transfer (MLCT) excitation at 400 nm. Data on [Ru(dmb)_3]~(2+) at 532 nm a region of net excited-state absorption, revealed biphasic decay kinetics (approx 120 fs and 5 ps) attributed to a combination of ~1MLCT -> ~3MLCT intersystem crossing and vibrational cooling dynamics. Dynamics for [Ru(dpb)_3]~(2+) under identical conditions revealed biphasic rise times in the region of the ligand-based #pi#~* implied by #pi#~* absorption at #lambda#_(probe) = 532 nm. Although the origin of the fast component (approx 200 fs) is not yet clear, the ca. 2 ps rise is assigned to rotation of the peripheral aryl ring and thus corresponds to the time scale for intraligand electron delocalization.
机译：过渡金属络合物[Ru（dmb）_3]〜（2+）和[Ru（dpb）_3]〜（2+），其中dmb为4,4'-二甲基-2,2'-联吡啶，dpb为4飞秒可见电子吸收光谱法研究了4，-二苯基-2,2'-联吡啶。光谱电化学测量与纳秒级时间分辨吸收光谱相结合，可以将激发态差分吸收光谱中的各种特征分配为＃pi＃〜*暗示的基于配体的＃pi＃〜*和配体-金属电荷转移（LMCT）。在[Ru（dpb）_3]〜（2+）中约530 nm处有一个独特的吸收特征被确定为热（并因此完全在配体内离域）激发态的光学标记。在400 nm的金属到配体电荷转移（MLCT）激发后，室温下CH_3CN溶液中的两个分子都获得了单波长和全光谱瞬态吸收数据。关于[Ru（dmb）_3]〜（2+）在532 nm净激发态吸收区域的数据，揭示了双相衰减动力学（约120 fs和5 ps）归因于〜1MLCT->〜3MLCT内部系统的组合穿越和振动冷却动力学。在相同条件下[Ru（dpb）_3]〜（2+）的动力学表明，＃pi＃〜*在#lambda #_（探针）的吸收暗示了基于配体的＃pi＃〜*区域的双相上升时间。 ＝ 532nm。尽管快速分量的起源（大约200 fs）尚不清楚，但大约2 ps的上升与周围芳基环的旋转有关，因此对应于配体内电子离域的时间标度。

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