title: Phenothiazine-anthraquinone donor-acceptor molecules: synthesis, electronic properties and DFT-TDDFT computational study.
abstract: Two donor-acceptor molecules with different pi-electron conjugative units, 1-((10-methyl-10H-phenothiazin-3-yl)ethynyl)anthracene-9,10-dione (AqMp) and 1,1'-(10-methyl-10H-phenothiazine-3,7-diyl)bis(ethyne-2,1-diyl)dianthracene-9,10-dione (Aq2Mp), have been synthesized and investigated for their photochemical and electrochemical properties. Density functional theory (DFT) calculations provide insights into their molecular geometry, electronic structures, and properties. These studies satisfactorily explain the electrochemistry of the two compounds and indicate that larger conjugative effect leads to smaller HOMO-LUMO gap (Eg) in Aq2Mp. Both compounds show ICT and pi --> pi* transitions in the UV-visible range in solution, and Aq2Mp has a bathochromic shift and shows higher oscillator strength of the absorption, which has been verified by time-dependent DFT (TDDFT) calculations. The differences between AqMp and Aq2Mp indicate that the structural and conjugative effects have great influence on the electronic properties of the molecules.
authors.affiliation: State Key Laboratory of Coordination Chemistry, Nanjing National Laboratory of Microstructures, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, 210093 P.R. China. wwzhang@nju.edu.cn
authors.forename: Wen-Wei
authors.initials: WW
authors.lastname: Zhang
authors.forename: Wei-Li
authors.initials: WL
authors.lastname: Mao
authors.forename: Yun-Xia
authors.initials: YX
authors.lastname: Hu
authors.forename: Zi-Qi
authors.initials: ZQ
authors.lastname: Tian
authors.forename: Zhi-Lin
authors.initials: ZL
authors.lastname: Wang
authors.forename: Qing-Jin
authors.initials: QJ
authors.lastname: Meng
mesh_terms: D000880:Anthraquinones / Q000138:chemical synthesis / Q000737:chemistry*; D003198:Computer Simulation; D004583:Electrons; D008956:Models, Chemical; D015394:Molecular Structure; D010640:Phenothiazines / Q000138:chemical synthesis* / Q000737:chemistry; D011789:Quantum Theory; D012997:Solvents / Q000737:chemistry; D013056:Spectrophotometry, Ultraviolet; D013997:Time Factors
chemical_list: D000880:Anthraquinones; D010640:Phenothiazines; D012997:Solvents; C031637:phenothiazine