Molecular, electronic structure and spectroscopic properties of MM quadruply bonded units supported by trans-6-carboethoxy-2-carboxylatoazulene ligands

Brian G. Alberding, Mikhail V. Barybin, Malcolm H. Chisholm, Terry L. Gustafson, Carly R. Reed, Randall E. Robinson, Nathan J. Patmore, Namrata Singh, Claudia Turro

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Abstract

The reaction between M2(TiPB)4 (M = Mo, W) where TiPB = 2,4,6-triisopropylbenzoate and 6-carboethoxy-2-azulenecarboxylic acid (2 equiv.) in toluene leads to the formation of complexes M2(TiPB) 2(6-carboethoxy-2-azulenecarboxylate)2. Compound I (M = Mo) is blue and compound II (M = W) is green. Both are air sensitive, hydrocarbon soluble species that gave the corresponding molecular ions in their mass spectra (MALDI-TOF). They show metal based oxidations and ligand based reductions. Electronic structure calculations (DFT and time dependent DFT) indicate that the two azulene carboxylate π systems are coupled by their interactions with the M2δ orbitals. Their intense colors arise from M2δ to azulene π* electronic transitions. While compound I exhibits weak emission at ∼ 900 nm, no emission has been detected for II. Both I and II have been studied by fs and ns transient absorption spectroscopy. The X-ray analysis of the molecular structure of II in the solid state confirmed the paddlewheel nature of its W2(O2C) 4 core and the trans orientation of the ligands.

Original languageEnglish
Pages (from-to)1979-1984
Number of pages6
JournalDalton Transactions
Volume39
Issue number8
Early online date13 Jan 2010
DOIs
Publication statusPublished - 28 Feb 2010
Externally publishedYes

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Alberding, B. G., Barybin, M. V., Chisholm, M. H., Gustafson, T. L., Reed, C. R., Robinson, R. E., ... Turro, C. (2010). Molecular, electronic structure and spectroscopic properties of MM quadruply bonded units supported by trans-6-carboethoxy-2-carboxylatoazulene ligands. Dalton Transactions, 39(8), 1979-1984. https://doi.org/10.1039/b919282d