Zhan Xiaowei, Risko Chad, Amy Fabrice, Chan Calvin, Zhao Wei, Barlow Stephen, Kahn Antoine, Brédas Jean-Luc, Marder Seth R
School of Chemistry and Biochemistry and Center for Organic Photonics and Electronics, Georgia Institute of Technology, Atlanta, Georgia 30332, USA.
J Am Chem Soc. 2005 Jun 29;127(25):9021-9. doi: 10.1021/ja051139i.
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.
我们展示了对四种1,1 - 二芳基 - 2,3,4,5 - 四苯基硅杂环戊二烯（芳基 = 苯基、2 - (9,9 - 二甲基芴基)、2 - 噻吩基、五氟苯基）电子结构的全面实验和理论表征。这些硅杂环戊二烯的固态电子亲和能和电离势分别使用逆光电子能谱（IPES）和光电子能谱（PES）进行测量；从密度泛函理论（DFT）水平计算得到的电子态密度与PES和IPES数据非常吻合。然后，基于电化学和/或光学数据的替代估计通过电子亲和能的直接IPES测量进行评估。我们还使用DFT计算了这些硅杂环戊二烯与其自由基阴离子之间电子转移反应的重组能。此外，利用光学数据以及电离势和电子亲和能数据来估计这些硅杂环戊二烯中激子的结合能。
