화학공학소재연구정보센터
Journal of the American Chemical Society, Vol.133, No.20, 8028-8039, 2011
Ortho-Branched Ladder-Type Oligophenylenes with Two-Dimensionally pi-Conjugated Electronic Properties
The synthesis, photochemical and electrochemical properties, and electronic structures of a series of star-shaped ladder-type oligophenylenes Sn (n = 7, 10, 13, 16, 19, and 22), induding one multibranched case S19mb, are reported and compared with the linear para-phenylene ladders Rn (n = 2-5 and 8) and the stepladder analogues SFn (n = 10, 16, and 22). The n value refers to the number of pi-conjugated phenylene rings. Functionalized isotruxenes are the key synthetic building blocks, and S22 is the largest mono dispersed ladder-type oligophenylene known to date. The Sn systems possess the structural rigidity of Rn and the ortho para phenylene connectivity of SFn. Consequently, Sn represents the first class of branched chromophores with fully two-dimensional conjugation in both ground- and excited-state configurations. Evidences include the excellent linear correlations for the optical 0-0 energies or the first oxidation potentials of Sn and Rn against the reciprocal of their n values, delocalized HOMO and LUMO based on density functional theory calculations, and molecule-like fluorescence anisotropy. The resulting model of effective conjugation plane (ECP) for the two-dimensional pi-conjugated systems compliments the concept of effective conjugation length (ECL) for one-dimensional oligomeric systems. Other implications of the observed structure property relationships are also included.