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Experimental and DFT/Time‐Dependent DFT Studies on Neutral and One‐Electron‐Reduced Quinoxaline and Pyrazine Precursors and Their Mononuclear (Pd II , Pt II ) Derivatives
Author(s) -
Donzello Maria Pia,
De Mori Giorgia,
Viola Elisa,
Futur David,
Fu Zhen,
Rizzoli Corrado,
Mannina Luisa,
Bodo Enrico,
Astolfi Maria Luisa,
Ercolani Claudio,
Kadish Karl M.
Publication year - 2014
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201402282
Subject(s) - quinoxaline , chemistry , pyrazine , density functional theory , pyridine , crystallography , electron paramagnetic resonance , spectral line , atomic orbital , computational chemistry , electron , stereochemistry , medicinal chemistry , nuclear magnetic resonance , organic chemistry , physics , quantum mechanics , astronomy
Electrochemical and UV/Vis spectral studies on the quinoxaline compound 2,3‐di(2‐pyridyl)‐6,7‐dicyano‐1,4‐quinoxaline, [(CN) 2 Py 2 Qx], its metallated derivatives [(CN) 2 Py 2 QxMCl 2 ] (M = Pd II , Pt II ) and their analogues sharing the dicyanopyrazine fragment are presented and discussed. X‐ray work on the new quinoxaline complex [(CN) 2 Py 2 QxPtCl 2 ] establishes that Pt II is coordinated to the pyridine N atoms (“py–py” coordination). The spectra of the 1– charged quinoxaline and pyrazine compounds show new intense absorptions in the region of 500–900 nm, and redshifted bands in the 250–400 nm region. By using DFT/time‐dependent DFT calculations, the spin density and spectral features of both couples of precursors and Pt II derivatives were investigated in terms of single‐electron excitations between the Kohn–Sham orbitals of the optimized structures in the gas and condensed phases. A detailed comparison is allowed of the experimental and calculated spectral features of the neutral and 1– charged species.