title: Electron affinities of 1,1-diaryl-2,3,4,5-tetraphenylsiloles: direct measurements and comparison with experimental and theoretical estimates.
abstract: We present a comprehensive experimental and theoretical characterization of the electronic structure of four 1,1-diaryl-2,3,4,5-tetraphenylsiloles (aryl = phenyl, 2-(9,9-dimethylfluorenyl), 2-thienyl, pentafluorophenyl). Solid-state electron affinities and ionization potentials of these siloles were measured using inverse-photoelectron spectroscopy (IPES) and photoelectron spectroscopy (PES), respectively; the density of electronic states obtained from calculations performed at the density functional theory (DFT) level corresponds very well to the PES and IPES data. The direct IPES measurements of electron affinity were then used to assess alternative estimates based on electrochemical and/or optical data. We also used DFT to calculate the reorganization energies for the electron-transfer reactions between these siloles and their radical anions. Additionally, optical data and ionization potential and electron affinity data were utilized to estimate the binding energies of excitons in these siloles.
authors.affiliation: School of Chemistry and Biochemistry and Center for Organic Photonics and Electronics, Georgia Institute of Technology, Atlanta, Georgia 30332, USA.
authors.forename: Xiaowei
authors.initials: X
authors.lastname: Zhan
authors.forename: Chad
authors.initials: C
authors.lastname: Risko
authors.forename: Fabrice
authors.initials: F
authors.lastname: Amy
authors.forename: Calvin
authors.initials: C
authors.lastname: Chan
authors.forename: Wei
authors.initials: W
authors.lastname: Zhao
authors.forename: Stephen
authors.initials: S
authors.lastname: Barlow
authors.forename: Antoine
authors.initials: A
authors.lastname: Kahn
authors.forename: Jean-Luc
authors.initials: JL
authors.lastname: Brédas
authors.forename: Seth R
authors.initials: SR
authors.lastname: Marder
mesh_terms: D004563:Electrochemistry; D004583:Electrons; D008956:Models, Chemical; D015394:Molecular Structure; D017646:Organosilicon Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D013057:Spectrum Analysis / Q000379:methods*; D013816:Thermodynamics
chemical_list: D017646:Organosilicon Compounds