Synthesis and experimental-computational characterization of nonlinear optical properties of triazacyclopentafluorene-coumarin derivatives

A series of novel 3-(2,2a,3-triazacyclopenta[jk]fluoren-1-yl)-2H-chromen-2-one derivatives 5a-c have been synthesized by [8 + 2] cycloaddition reaction between the corresponding 3-(imidazo[1,2-a]pyrimidines)-2-yl)-2H-chromen-2-one 4a-c with 2-(trimethylsilyl)phenyl triflates as benzyne precursor in 65-80% yields. The strategic incorporation of triazacyclopentafluorene group at the 3-position of the coumarin molecules resulted in dyes with excellent nonlinear optical properties. The nonlinear optical properties of third order (compounds 5a-c) were studied using Z-scan technique. The high nonlinear response is of 10(-7) cm(2)/W order. The nonlinearity of the compounds is an indication of a promising material for applications at low power, such as optical switching, waveguides, nonlinear contrast phase, among others. Theoretical results of HOMO-LUMO gaps and oscillator strengths are used to rationalize the high efficiency of the novel compound in the nonlinear optical behavior. In particular, 5b displays the best nonlinear optical properties and at the same time the smaller HOMO-LUMO gap and the highest oscillator strength. (C) 2016 Elsevier B.V. All rights reserved.