title: Hybrid organic semiconductors including chalcogen atoms in pi-conjugated skeletons. Tuning of optical, redox, and vibrational properties by heavy atom conjugation.
abstract: In this work, the interactions between heteroatoms (S, Se, and Te) and conjugated skeletons are analyzed. The study is carried out by using electronic absorption and fluorescence spectroscopies, electrochemistry, vibrational Raman spectroscopy, and theoretical calculations in the framework of DFT and TD-DFT theories. Optical spectra are described in terms of one-electron promotions between orbitals around the energy gap. Electrochemistry, in the framework of the Koopman's approach, is also interpreted. The vibrational Raman spectra are assigned to molecular modes and the evolution changing the heteroatom is addressed and an effective tuning of these properties is found. Part of this modulation is associated with local electronic interactions depending on the relative S, Se, and Te electronegativities. Unconventional long-range heteroatom-heteroatom interactions have been proposed which arise from the existence of effective pi-conjugated channels. The molecular level understanding of structure-property relationships in these organic/inorganic semiconductors are of great interest in the interdisciplinary area of material science.
authors.affiliation: Department of Physical Chemistry, University of Malaga, Campus de Teatinos s/n, Malaga 29071, Spain. casado@uma.es
authors.forename: Juan
authors.initials: J
authors.lastname: Casado
authors.forename: María
authors.initials: M
authors.lastname: Moreno Oliva
authors.forename: Mari C
authors.initials: MC
authors.lastname: Ruiz Delgado
authors.forename: Rocío
authors.initials: R
authors.lastname: Ponce Ortiz
authors.forename: J
authors.initials: J
authors.lastname: Joaquín Quirante
authors.forename: Juan T
authors.initials: JT
authors.lastname: López Navarrete
authors.forename: Kazuo
authors.initials: K
authors.lastname: Takimiya
authors.forename: Tetsuo
authors.initials: T
authors.lastname: Otsubo
mesh_terms: D018011:Chalcogens / Q000737:chemistry*; D003198:Computer Simulation; D004563:Electrochemistry; D008956:Models, Chemical; D015394:Molecular Structure; D055095:Optics and Photonics; D009942:Organometallic Compounds / Q000737:chemistry*; D016566:Organoselenium Compounds / Q000737:chemistry; D010084:Oxidation-Reduction; D012666:Semiconductors; D012680:Sensitivity and Specificity; D013050:Spectrometry, Fluorescence / Q000379:methods; D013059:Spectrum Analysis, Raman / Q000379:methods; D013457:Sulfur Compounds / Q000737:chemistry; D013691:Tellurium / Q000737:chemistry; D014732:Vibration
chemical_list: D018011:Chalcogens; D009942:Organometallic Compounds; D016566:Organoselenium Compounds; D013457:Sulfur Compounds; D013691:Tellurium