Research School of Chemistry, Australian National University, Canberra, ACT 2601, Australia.
School of Chemical and Material Engineering, Jiangnan University, Wuxi, 214122, P. R. China.
Angew Chem Int Ed Engl. 2023 Jul 3;62(27):e202301754. doi: 10.1002/anie.202301754. Epub 2023 May 9.
Porphyrins are important macrocycles with applications in several areas including therapy, catalysis, and sensing. Strong nonlinear optical (NLO) responses are the key to fully exploiting the potential of these biocompatible molecules. We herein report that certain metal-alkynyl donor/nitro acceptor-functionalized porphyrins are attractive candidates for NLO applications. We show that specific examples exhibit record quadratic optical nonlinearity, exceptional two-photon absorption, and outstanding three-photon absorption, and we report the first porphyrins that exhibit four-photon absorption. The two-, three-, and four-photon absorption maxima are found at the corresponding multiples of linear absorption bands that time-dependent density functional theory assigns as admixtures of porphyrin-localized π*←π and donor-porphyrin to porphyrin-acceptor charge-transfer transitions.
卟啉是一类重要的大环化合物，在治疗、催化和传感等多个领域都有应用。强非线性光学（NLO）响应是充分发挥这些生物相容性分子潜力的关键。本文报道了某些金属-炔基给体/硝基受体功能化卟啉是 NLO 应用的有吸引力的候选材料。我们表明，某些实例表现出创纪录的二次光学非线性、异常的双光子吸收和优异的三光子吸收，并报道了首例具有四光子吸收的卟啉。双光子、三光子和四光子吸收的最大值出现在相应的线性吸收带的整数倍处，这与时间依赖的密度泛函理论所分配的卟啉局域π*←π 和给体-卟啉到卟啉-受体电荷转移跃迁的混合物相对应。
