Synthesis, Structure, and Significant Energy Gap Modulation of Symmetrical Silafluorene-Cored Tetracyanobutadiene and Tetracyanoquinodimethane Derivatives.

Abstract

A series of symmetrical tetracyanobutadiene and tetracyanoquinodimethane derivatives with a D-A-D'-A-D structural configuration and silafluorene core (D') were designed and readily synthesized via a [2+2] cycloaddition-retroelectrocyclization (CA-RE) reaction. We found that the photophysical properties and HOMO and LUMO energy levels and gaps of the silafluorene derivatives could be profoundly remolded through CA-RE reactions and modulated by varying the peripheral donor units from phenyl, m-dimethoxyphenyl, and N,N-dimethylaniline to triphenylamine groups. After CA-RE reactions, the HOMO-LUMO gaps of 1a-1j are in the range of 1.75-2.78 eV, with significant decreases of 0.52-1.46 eV compared to those of the parent silafluorene compounds 2a-2j. The intriguing crystal structures of 1f and 1j were analyzed and elucidated to show their unique potential porosity. The stability, electrochemical, and computational studies were systematically performed to unveil the reshaped electron-donating and -withdrawing nature in one molecular system. 1h-1j with peripherally strong amino donors exhibit an intense and broad intramolecular charge transfer absorption band in the near-infrared region from 550 to 900 nm. The molecular design and synthesis reported here broaden the types and fields of D-A molecular systems for potential applications in organic optoelectronic devices.