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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >A comparative study of the redox and excited state properties of (nBu _4N)_2[Mo_6X_(14)] and (nBu _4N_)2[Mo_6X_8(CF_3COO) _6] (X = Cl, Br, or I)
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A comparative study of the redox and excited state properties of (nBu _4N)_2[Mo_6X_(14)] and (nBu _4N_)2[Mo_6X_8(CF_3COO) _6] (X = Cl, Br, or I)

机译：（nBu _4N）_2 [Mo_6X_（14）]和（nBu _4N_）2 [Mo_6X_8（CF_3COO）_6]（X = Cl，Br或I）的氧化还原和激发态性质的比较研究

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The excited-state dynamics, luminescence, and redox properties of a series of hexanuclear molybdenum cluster complexes, (nBu_4N) _2[Mo_6X_(14)] and (nBu_4N) _2[Mo_6X_8(CF_3COO)_6] (X = Cl, Br, or I), were investigated. Substitution of the apical halogen ligands for the trifluoroacetate ligands increased the oxidation potentials and induced a blue shift in the absorption and luminescence bands as well as a considerable increase in the luminescence quantum yields for heavy inner ligands. Time-resolved transient absorption measurements showed that the intersystem crossing from the excited singlet states is ultrafast with time constants ranging between <120 fs and 1.68 ps and leads to hot triplet states. The following cooling occurred at a ps time scale and was assigned to electronic redistribution within the emissive triplet state sublevels. The formation of singlet oxygen, O_2(~1Δ_g), suggested earlier on the basis of photooxidation experiments for some complexes, was revised by direct measurements of O_2(~1Δ_g) phosphorescence. We showed the effects of the attached ligands on key physico-chemical and photophysical parameters of the title complexes. The synthesis and structural characterisation of a new cluster complex, (nBu 4N)2[Mo_6Br_8(CF_3COO) _6], completed the series. Our results demonstrated that the complexes with heavy inner ligands (Br, I) and apical trifluoroacetate ligands were photochemically and electrochemically stable, highly luminescent, and good sensitisers of O_2(~1Δ_g).
机译：一系列六核钼簇复合物（nBu_4N）_2 [Mo_6X_（14）]和（nBu_4N）_2 [Mo_6X_8（CF_3COO）_6]的激发态动力学，发光和氧化还原特性（X = Cl，Br或我），进行了调查。顶端卤素配体取代三氟乙酸酯配体增加了氧化电位，并引起了吸收带和发光带的蓝移以及重的内部配体的发光量子产率的显着提高。时间分辨的瞬态吸收测量结果表明，与激发单重态交叉的系统间速度极快，时间常数在<120 fs和1.68 ps之间，并导致热三重态。随后的冷却以ps的时间尺度发生，并分配给了发光三重态子级别内的电子重新分布。通过对O_2（〜1Δ_g）磷光的直接测量，修正了先前根据某些配合物的光氧化实验建议的单线态氧O_2（〜1Δ_g）的形成。我们显示了附着的配体对标题配合物的关键物理化学和光物理参数的影响。新的簇复合物（nBu 4N）2 [Mo_6Br_8（CF_3COO）_6]的合成和结构表征完成了该系列。我们的结果表明，具有重内部配体（Br，I）和顶端三氟乙酸酯配体的配合物具有光化学和电化学稳定性，高发光性，并且是O_2（〜1Δ_g）的良好敏化剂。

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