Redox reaction was photoinduced on metal nanoparticle (NP) with diruthenium complexes absorbing on the surface. Surface enhanced Raman scattering (SERS) was employed to detect the vibrational wavenumber of the Ru–Ru stretching mode ν_Ru–Ru,str. During reaction, the local environment remains roughly unaltered; the variation of bonding strength of Ru–Ru related to its valence state can be measured. The heterometal extended metal atom chain (EMAC) complexes diruthenium nickel dipyridylamide [Ru₂Ni(dpa)₄Cl₂]^0,1+ (dpa = dipyridylamide) display the Raman ν_Ru–Ru,str at 327 (broad) and 333 cm^–1 in solid form for the neutral and oxidized complexes, respectively, but red-shift to 312 cm^–1 on gold NP substrate and to 328 cm^–1 on AgNP. According to the oxidation potentials from voltammogram, and the Raman shifts obtained for the model complex Ru₂(OAc)₄Cl we assign the diruthenium core with charge +5/+4 and +6, respectively for the neutral and oxidized diruthenium nickel dipyridylamide in solid form. On substrate AuNP the hot electrons produced to fill in the antibonding orbital, the Ru₂⁴⁺ π*⁴ core with weak Ru–Ru bonding was formed and on AgNP the oxidized complex was reduced to neutral form. For pentanuclear EMAC [Ni–Ru₂-Ni₂(tpda)₄(NCS)₂] (tpda = tripyridyldiamide) ν_Ru–Ru,str is at 337 cm^–1 and SERS band peaked at 328 cm^–1. We assign the Ru₂⁶⁺ core in solid and reduction by NPs to form Ru₂⁵⁺.

中文翻译：

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使用氧化还原反应和表面增强拉曼散射测定钌部分的价态：在杂金属扩展金属原子链钌镍配合物中的应用

氧化还原反应在金属纳米粒子（NP）上发生光诱导，并且钌络合物吸收在表面上。使用表面增强拉曼散射（SERS）来检测Ru-Ru拉伸模式νRu _-Ru，str的振动波数。在反应期间，当地环境大致保持不变；可以测量Ru-Ru的键合强度与其价态有关的变化。杂金属延伸金属原子链（EMAC）络合物二钌镍二吡啶^酰胺[Ru ₂ Ni（dpa）₄ Cl ₂ ] ^0,1+（dpa =二吡啶^酰胺）在327（宽）和333 cm处显示拉曼^νRu _–Ru，str ^–1分别以固体形式存在于中性和氧化配合物中，但在金NP底物上红移至312 cm ^–1，在AgNP上红移至328 cm ^–1。根据伏安图的氧化电势，以及模型复合物Ru ₂（OAc）₄ Cl的拉曼位移，我们为中和氧化的二钌镍二吡啶基酰胺分别分配了带有+ 5 / + 4和+6电荷的二钌核。固体形式。在基底AuNP上产生的热电子填充反键轨道，形成具有弱Ru-Ru键的Ru ₂ ⁴⁺ π* ⁴核，在AgNP上，氧化的络合物还原为中性形式。对于五核EMAC [Ni–Ru ₂ -Ni₂（tpda）₄（NCS）₂ ]（tpda =三吡啶_基二酰胺）νRu _–Ru，str在337 cm ^–1处，SERS谱带在328 cm ^–1处达到峰值。我们将固体中的Ru ₂ ⁶⁺核分配并通过NP还原以形成Ru ₂ ⁵⁺。