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Surface Enhanced Raman Spectroelectrochemistry of a μ-Oxo Triruthenium Acetate Cluster: An Experimental and Theoretical Approach
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2015-09-22 00:00:00 , DOI: 10.1021/acs.inorgchem.5b01751 Jonnatan J. Santos 1 , Romulo A. Ando 1 , Sergio H. Toma 1 , Paola Corio 1 , Koiti Araki 1 , Henrique E. Toma 1
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2015-09-22 00:00:00 , DOI: 10.1021/acs.inorgchem.5b01751 Jonnatan J. Santos 1 , Romulo A. Ando 1 , Sergio H. Toma 1 , Paola Corio 1 , Koiti Araki 1 , Henrique E. Toma 1
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Surface enhanced Raman spectroelectrochemistry (SERS) spectroelectrochemistry provides a very sensitive technique to investigate the vibrational characteristics of coordination compounds and their particular behavior under the influence of plasmonic surfaces, concomitant with the exploitation of their redox properties and electronic spectra. The results, however, depend upon the mechanisms involved in the intensification of Raman spectra associated with the electromagnetic, resonance Raman and charge-transfer excitation at the Fermi levels. By probing the model complex [(Ru3O)(CH3COO)6(4,4′-bipy)3]n (n = 1, 0, −1) adsorbed onto rough gold electrode surfaces, contrasting SERS profiles were obtained at several successive redox potentials and oxidation states, which enables a critical discussion on the role of the complex interaction with the gold surface, and the influence of the specific electronic bands in the triruthenium acetate cluster. Density functional theory (DFT) and time-dependent DFT calculations were carried out for the complex bound to an Au20 cluster to show the participation of active lowest unoccupied molecular orbital levels centered on the gold atoms. The corresponding charge-transfer band was predicted around 1200 nm, which supports a charge-transfer interpretation for the SERS response observed at λexc = 1064 nm. The selective enhancement of the vibrational modes was discussed based on the Raman theoretical calculations.
中文翻译：
μ-Oxo醋酸三钌盐簇的表面增强拉曼光谱电化学：一种实验和理论方法
表面增强拉曼光谱电化学（SERS）光谱电化学提供了一种非常灵敏的技术，用于研究配体化合物在等离子表面的影响下的振动特性及其特殊行为，同时还利用了它们的氧化还原特性和电子光谱。然而，结果取决于拉曼光谱增强与费米能级的电磁，共振拉曼和电荷转移激发有关的机制。通过探测模型复合物[（Ru 3 O）（CH 3 COO）6（4,4'-bipy）3 ] n（n= 1，0，-1）吸附在粗糙的金电极表面上，在几个连续的氧化还原电势和氧化态下获得了对比的SERS分布图，这使得能够就与金表面的复杂相互作用的作用以及金属的影响进行批判性的讨论。醋酸三钌簇中的特定电子带。对结合到Au 20团簇上的配合物进行了密度泛函理论（DFT）和时变DFT计算，以显示以金原子为中心的活性最低未占据分子轨道能级的参与。预计相应的电荷转移带在1200 nm左右，这支持在λexc处观察到的SERS响应的电荷转移解释。= 1064 nm。基于拉曼理论计算，讨论了振动模态的选择性增强。
更新日期：2015-09-22
中文翻译：
μ-Oxo醋酸三钌盐簇的表面增强拉曼光谱电化学：一种实验和理论方法
表面增强拉曼光谱电化学（SERS）光谱电化学提供了一种非常灵敏的技术，用于研究配体化合物在等离子表面的影响下的振动特性及其特殊行为，同时还利用了它们的氧化还原特性和电子光谱。然而，结果取决于拉曼光谱增强与费米能级的电磁，共振拉曼和电荷转移激发有关的机制。通过探测模型复合物[（Ru 3 O）（CH 3 COO）6（4,4'-bipy）3 ] n（n= 1，0，-1）吸附在粗糙的金电极表面上，在几个连续的氧化还原电势和氧化态下获得了对比的SERS分布图，这使得能够就与金表面的复杂相互作用的作用以及金属的影响进行批判性的讨论。醋酸三钌簇中的特定电子带。对结合到Au 20团簇上的配合物进行了密度泛函理论（DFT）和时变DFT计算，以显示以金原子为中心的活性最低未占据分子轨道能级的参与。预计相应的电荷转移带在1200 nm左右，这支持在λexc处观察到的SERS响应的电荷转移解释。= 1064 nm。基于拉曼理论计算，讨论了振动模态的选择性增强。
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