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

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 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 and 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 and 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.