Alberding Brian G, Chisholm Malcolm H, Durr Christopher B, Gallucci Judith C, Ghosh Yagnaseni, Spilker Thomas F
The Ohio State University, 100 West 18th Avenue, Columbus, OH 43210, USA.
Dalton Trans. 2014 Aug 7;43(29):11397-403. doi: 10.1039/c4dt01073f. Epub 2014 Jun 16.
From the reactions between Mo2(T(i)PB)4, where T(i)PB = 2,4,6-triisopropylbenzoate and two equivalents of the carboxylic acid LH (LH = 4-nitrobenzoic acid and 4'-nitro[1,1'-biphenyl]-4-carboxylic acid) the compounds trans-M2(T(i)PB)2L2 have been prepared: I (L = 4-nitrobenzoate and M = Mo), II (L = 4'-nitro-1,1'-biphenylcarboxylate and M = Mo) and III (L = 4-nitrobenzoate and M2 = MoW). The compounds have been characterized by (1)H NMR, UV-Vis and steady state emission spectroscopy, ns and fs transient absorption spectroscopy and cyclic voltammetry. These data are compared with predictions based on electronic structure calculations on model compounds where T(i)PB is substituted for formate. Together these data indicate stronger ground-state coupling of the Mo2δ and ligand π* systems in I relative to II but this order is reversed in the photo excited S1(1)MLCT state. Attempts to prepare the W2 containing analogs were unsuccessful.
通过Mo2(T(i)PB)4（其中T(i)PB = 2,4,6 - 三异丙基苯甲酸酯）与两当量的羧酸LH（LH = 4 - 硝基苯甲酸和4'-硝基[1,1'-联苯]-4 - 羧酸）之间的反应，制备了化合物反式 - M2(T(i)PB)2L2：I（L = 4 - 硝基苯甲酸酯且M = Mo）、II（L = 4'-硝基 - 1,1'-联苯羧酸酯且M = Mo）和III（L = 4 - 硝基苯甲酸酯且M2 = MoW）。这些化合物已通过1H NMR、紫外 - 可见光谱和稳态发射光谱、纳秒和飞秒瞬态吸收光谱以及循环伏安法进行了表征。这些数据与基于用T(i)PB取代甲酸酯的模型化合物的电子结构计算的预测结果进行了比较。这些数据共同表明，相对于II，I中Mo2δ和配体π*体系的基态耦合更强，但在光激发的S1(1)MLCT态中这种顺序相反。制备含W2类似物的尝试未成功。
