Impact of different auxochromes hydroxyl and methyl on two photon absorption coefficients and ultrafast dynamics of near-infrared hemicyanine dyes

There is immense interest in the design of organic nonlinear optical (NLO) chromophores for optical limiting and bioimaging applications. In this work, two near-infrared hemicyanine compounds which are named 2-(2-(3-Hydroxy-8,9-dihydro-7H-pyrido[1,2-a]quinazolin-10-yl)vinyl)-1,1-dimethyl-3-propy l-1H-benzo[e]indol-3-ium iodide (Hemicyanine1) and 1,1-Dimethyl-2-(2-(3-methyl-8,9-dihydro-7Hpyrido[1,2-a]quinazolin-10-yl)vinyl)-3-propyl-1H-benzo[e]indol-3-ium iodide (Hemicyanine2) were synthesized. The difference between Hemicyanine1 and Hemicyanine2 is that one of the auxochrome is hydroxyl and the other is methyl. The third-order nonlinear optical absorption properties of Hemicyanine1 and Hemicyanine2 were investigated using broadband Z-scan measurements at nanosecond time regime. The Z-scan results demonstrate that both chromophores have reverse-saturable absorption (RSA), while the NLO response of Hemicyanine2 is significantly stronger than Hemicyanine1. The corresponding physical mechanism were studied via femtosecond transient absorption (TA) spectroscopy. The results of femtosecond TA measurement demonstrate that the lifetime of excited state of Hemicyanine2 is considerably longer than that of Hemicyanine1. Our study indicated that the auxochrome is critically important in optimizing the NLO response and excited-state lifetime of hemicyanine chromophores for photonic applications.