期刊
STRUCTURAL CHEMISTRY
卷 25, 期 2, 页码 625-634出版社
SPRINGER/PLENUM PUBLISHERS
DOI: 10.1007/s11224-013-0332-z
关键词
Monoamino-9,10-anthraquinone derivatives; Acid-base properties; UV-Vis spectrophotometry; Spectrophotometric titrations; Cyclic voltammetry; DFT calculations
资金
- State Funds for Scientific Research through National Center for Science [NN204 122 640]
- Polish Ministry of Science and Higher Education [DS/530-8221-D186-13]
- system project InnoDoktorant - Scholarships for PhD students, Vth edition
- European Union in the frame of the European Social Fund
- Wroclaw Center for Networking and Supercomputing [209]
1-Amino-, 1-ethylamino-, and 1-(diethylamino)-anthraquinone were characterized by UV-Vis spectroscopy, acid-base titration, electrochemical methods, and quantum-chemical (QM) calculations at the B3LYP/6-31 ++G(**) level. Acid-base titration and the relative differences between the free energies of the basic and acidic forms of the studied species show that 1-(diethylamino)anthraquinone is the strongest base in an acetonitrile solution. Moreover, the structural differences between the B3LYP-optimized neutral and protonated anthraquinones, notably the presence or the absence of internal hydrogen bonds, account well for the sequence of the measured/calculated basicity. The basicity of the investigated compounds strongly influences their electrochemical properties in acetonitrile. Indeed, the cyclic voltammograms of 1-aminoanthraquinone and 1-(ethylamino)anthraquinone display two well-resolved reduction waves that indicate a two-step reduction process (EE mechanism). On the other hand, the electroreduction of 1-(diethylamino)anthraquinone becomes complicated by the interaction of its reduced forms with traces of water present in an acetonitrile solution (ECE mechanism). The mechanism of this reaction is proposed, and its possibility to occur is examined based on QM calculations.
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