Influence of ligand substitution on excited state structural dynamics in Cu(I) bisphenanthroline complexes.
Influence of ligand substitution on excited state structural dynamics in Cu(I) bisphenanthroline complexes.
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配体取代对 Cu(I) 双菲咯啉配合物激发态结构动力学的影响。
DOI：
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发表时间：
2010
影响因子：
3.3
通讯作者：
Lin X. Chen
中科院分区：
文献类型：
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作者：
Jenny V. Lockard;Sanaz Kabehie;J. Zink;G. Smolentsev;A. Soldatov;Lin X. Chen
本研究探讨了空间位阻和激发态溶剂连接对Cu(I)二亚胺配合物激发态动力学的影响。利用飞秒瞬态吸收光谱测量了Cu(I)bis（3,8-二（乙基三硝基）-1,10-菲罗啉）[Cu(I)(detp)(2)]（+）的超快激发态动力学。与Cu(I)双（1,10-菲罗啉）、[Cu(I)(phen)(2)]（+）和Cu(I)双（2-9-二甲基-1,10-菲罗啉）、[Cu(I)(dmp)(2)]（+）模型配合物的稳态电子吸收光谱和测量寿命进行了比较，以确定不同取代模式的菲罗啉配体对与金属到配体电荷转移激发态相关的结构动力学的影响。[Cu(I)(detp)(2)]（+）和[Cu(I)(phen)(2)]（+）的激发态寿命在配位和非配位溶剂中都有相似之处，这是由于在2位和9位上缺乏取代的空间位阻。本文报道了[Cu(I)(detp)(2)]（+）、[Cu(I)(phen)(2)]（+）和[Cu(I)(dmp)(2)]（+）的溶液相x射线吸收光谱，并采用有限差分法计算了用于确定溶液中基态二面角畸变程度的方法，并解释了XANES区域观察到的前边缘特征。
This study explores the influences of steric hindrance and excited state solvent ligation on the excited state dynamics of Cu(I) diimine complexes. Ultrafast excited state dynamics of Cu(I)bis(3,8-di(ethynyltrityl)-1,10-phenanthroline) [Cu(I)(detp)(2)](+) are measured using femtosecond transient absorption spectroscopy. The steady state electronic absorption spectra and measured lifetimes are compared to those of Cu(I)bis(1,10-phenanthroline), [Cu(I)(phen)(2)](+), and Cu(I)bis(2-9-dimethyl-1,10-phenanthroline), [Cu(I)(dmp)(2)](+), model complexes to determine the influence of different substitution patterns of the phenanthroline ligand on the structural dynamics associated with the metal to ligand charge transfer excited states. Similarities between the [Cu(I)(detp)(2)](+) and [Cu(I)(phen)(2)](+) excited state lifetimes were observed in both coordinating and noncoordinating solvents and attributed to the lack of steric hindrance from substitution at the 2- and 9-positions. The solution-phase X-ray absorption spectra of [Cu(I)(detp)(2)](+), [Cu(I)(phen)(2)](+), and [Cu(I)(dmp)(2)](+) are reported along with finite difference method calculations that are used to determine the degree of ground state dihedral angle distortion in solution and to account for the pre-edge features observed in the XANES region.