4-Nitrophenyl- and 4'-nitro-1,1'-biphenyl-4-carboxylates attached to Mo2 quadruple bonds: ground versus excited state M2δ-ligand conjugation

• Published in: Dalton transactions : an international journal of inorganic chemistry 2014-08, Vol.43 (29), p.11397-11403
• Main Authors: Alberding, Brian G, Chisholm, Malcolm H, Durr, Christopher B, Gallucci, Judith C, Ghosh, Yagnaseni, Spilker, Thomas F
• Format: Article
• Language: English
• ISSN: 1477-9226; 1477-9234
• DOI: 10.1039/c4dt01073f

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.