Photoinduced Charge Transfer and Bimetallic Bond Dissociation of a Bi-W Complex in Solution.,The Journal of Physical Chemistry Letters

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Photoinduced Charge Transfer and Bimetallic Bond Dissociation of a Bi-W Complex in Solution.
The Journal of Physical Chemistry Letters ( IF 4.8 ) Pub Date : 2020-08-20 , DOI: 10.1021/acs.jpclett.0c02380
Sean A Boulanger ₁ , Liangdong Zhu ₁ , Longteng Tang ₁ , Sumit Saha ₁ , Douglas A Keszler ₁ , Chong Fang ₁

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Organometallic complexes including metal carbonyls have been widely utilized in academic and industrial settings for purposes ranging from teaching basic catalytic reactions to developing state-of-the-art electronic circuits. Characterization of these materials can be obtained via steady-state measurements; however, the intermediate photochemical events remain unclear, hindering effective and rational molecular engineering methods for new materials. We employed femtosecond transient absorption (fs-TA) and ground-state femtosecond stimulated Raman spectroscopy (FSRS) on triphenylbismuth–tungsten pentacarbonyl complex, a solution precursor for bimetallic oxide thin films. Upon 280 nm excitation into a charge-transfer band, an ultrafast bimetallic bond dissociation occurs within ∼140 fs. The subpicosecond nondiffusive solvation events are followed by ∼10 ps (15 ps) methanol (ethanol) complexation of the nascent tungsten pentacarbonyl intermediate, which mainly undergoes vibrational relaxation after crossing into a hot ground state. The trans ligand to axial CO is revealed to play a key role in the electronic and vibrational structure and dynamics of the complex. These findings could power rational design of bimetallic and functional solution precursors for the light-driven nanopatterning of thin films.

中文翻译：

溶液中Bi-W配合物的光诱导电荷转移和双金属键解离。

包括羰基金属在内的有机金属络合物已在学术和工业环境中得到广泛应用，其用途包括从教授基本的催化反应到开发最新的电子电路。这些材料的表征可以通过稳态测量获得。然而，中间的光化学事件仍然不清楚，阻碍了新材料的有效和合理的分子工程方法。我们在三苯基铋-钨五羰基络合物（双金属氧化物薄膜的溶液前体）上采用了飞秒瞬态吸收（fs-TA）和基态飞秒激发拉曼光谱（FSRS）。在280 nm激发进入电荷转移带后，超快双金属键解离在约140 fs内发生。亚皮秒的非扩散溶剂化事件之后，是新生的五羰基钨中间体的约10 ps（15 ps）甲醇（乙醇）络合物，该络合物在进入热基态后主要经历振动弛豫。的揭示了轴向CO的反式配体在配合物的电子和振动结构以及动力学中起关键作用。这些发现可以为双金属和功能溶液前体的合理设计提供动力，以进行薄膜的光驱动纳米构图。

更新日期：2020-09-18

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