π-Extended Octupolar Cyclized Indole Tetramer and Trimer Derivatives with Second- and Third-Order Nonlinear Optical Properties.

Abstract

Several aromatic-fused octupolar tetraindole (TTI) and triindole (TI) derivatives have been synthesized via POCl3-promoted cyclopolymerization of the aromatic-fused oxindoles. As a result, the terminal phenyls of TTI and TI are fused with the phenyl group, indenyl group, and benzothienyl group separately in the π-extended target compounds TTIp and TIp, TTIid and TIid, and TTIbt and TIbt (including pairs of syn- and anti-isomers). Single-crystal X-ray diffraction disclosed that the tetramer syn-TTIbt keeps an S4-symmetric architecture and crystallizes in the P42/n space group. With the extension of the π-conjugation, the absorption and emission bands of the above tetramers and trimers are remarkably red-shifted. The second-order nonlinear optical (NLO) coefficients (β value) of syn-TTIbt and anti-TTIbt have been calculated to be 1.5 and 2.1 times that of their parent compound TTI, respectively. In the domain of the third-order NLO, the two-photon absorption sections (δ value) of syn-TIbt and anti-TIbt have been measured to be 37 and 102 times that of TI, respectively. These results indicate that the π-extension strategy here is successful, and the anti-isomers have better NLO properties and better π-conjugation than their corresponding syn-isomers.