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Issue 7, 2016
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Solvent, coordination and hydrogen-bond effects on the chromic luminescence of the cationic complex [(phen)(H2O)Re(CO)3]+

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Abstract

The [(phen)(H2O)Re(CO)3]+(CF3SO3) salt, 1+(CF3SO3), has been crystallized in the form of two new solvates, [(phen)(H2O)Re(CO)3]+(CF3SO3)·(C4H8O)0.5 and [(phen)(H2O)Re(CO)3]+(CF3SO3)·CH2Cl2. The structures, as determined by single-crystal X-ray diffraction, show intense hydrogen bonding between the coordinated water molecule on 1+ and the triflate oxygen atoms, with Owater⋯Otriflate in the range from 2.608(13) to 2.972(13) Å. This feature, to the best of our knowledge, is preserved for each solvate of 1+(CF3SO3). The spectroscopic characterization of 1+(CF3SO3) in solution together with DFT and TD-DFT results suggest that its photophysical behavior depends on the solvent polarity, as normally found for MLCT, but additionally, on the coordinating and hydrogen bonding ability of the solvent. The results suggest that in low-polarity, non-coordinating and non-hydrogen bonding solvents, the intimate association observed in the solid between 1+(CF3SO3) is preserved, in contrast to coordinating solvents that may replace the coordinated water. Finally, weakly coordinating but hydrogen bonding solvents may dissociate the ionic pair units. The sum of all these effects leads to an apparent unusual solvent dependency of the luminescence emission with hypsochromic or bathochromic shifts depending on the coordinating ability of the solvent.

Graphical abstract: Solvent, coordination and hydrogen-bond effects on the chromic luminescence of the cationic complex [(phen)(H2O)Re(CO)3]+

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Publication details

The article was received on 18 Mar 2016, accepted on 19 May 2016 and first published on 19 May 2016


Article type: Paper
DOI: 10.1039/C6NJ00885B
Citation: New J. Chem., 2016,40, 6451-6459
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    Solvent, coordination and hydrogen-bond effects on the chromic luminescence of the cationic complex [(phen)(H2O)Re(CO)3]+

    P. Mella, K. Cabezas, C. Cerda, M. Cepeda-Plaza, G. Günther, N. Pizarro and A. Vega, New J. Chem., 2016, 40, 6451
    DOI: 10.1039/C6NJ00885B

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