Journal
JOURNAL OF MOLECULAR STRUCTURE
Volume 1150, Issue -, Pages 531-539Publisher
ELSEVIER SCIENCE BV
DOI: 10.1016/j.molstruc.2017.09.018
Keywords
Cobalt(II); Nickel(II) and copper(II); Thiophene; Diketonate complex; Single-crystal X-ray diffraction; DFT and TD-DFT calculations
Categories
Funding
- Fondo Nacional de Desarrollo Cientifico y Tecnologico [FONDECYT (Chile)] [1140903]
- FONDEQUIP [EQM130154]
- Vice-rrectoria de Investigacion y Estudios Avanzados, Pontificia Universidad Catolica de Valparaiso, Chile
- CNRS
- Universite de Rennes 1
- GENCI-CINES French national computer center [a0010807367]
- CONICYT (Chile) [21120098]
- GENCI-IDRISS French national computer center [a0010807367]
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In this work, we present the synthesis of the unsymmetrical beta-diketone 1-(2-thienyl)-3-(4-fluorophenyl)-propane-1,3-dione (HL) and its corresponding Co(II), Ni(II) and Cu(II) bis(beta-diketonato) complexes 1-3, respectively. The four new compounds were isolated in good yields (65-70%), and characterized by mass spectrometry, elemental analysis, FF-IR and UV-Vis spectroscopy and, in the case of HL, by H-1: C-13 and F-19 NMR spectroscopy. In addition, the molecular identities and the geometries of the beta-diketone HL and complex 3 were confirmed by X-ray diffraction analysis. The dicarbonyl derivative HL does exist as the diketo tautomeric form in DMSO solution and as its keto-enol tautomer in the solid-state with the OH group adjacent to the 4-fluorophenyl unit. The keto-enol isomer was computed to be more stable by 8.2 kcal/mol in free energy at room temperature. In 3, the Cu(II) center adopts a perfect square-planar geometry. Two reduction processes were observed in the cyclovoltammogram of 3 at -1.30 and -1.80 V vs. Fc/Fc(+), with copper deposit on the surface of the electrode. DFT and TD-DFT calculations on HL and complex 3 allow rationalizing their stability, bonding and properties. (C) 2017 Elsevier B.V. All rights reserved.
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