Zhang Xiang-Biao, Feng Ji-Kang, Ren Ai-Min, Sun Chia-Chung
State Key Laboratory of Theoretical and Computational Chemistry, Institute of Theoretical Chemistry, Changchun, 130023, China.
J Phys Chem A. 2006 Nov 9;110(44):12222-30. doi: 10.1021/jp062350z.
The electronic structures, one-photon absorption (OPA), and two-photon absorption (TPA) properties of a series of ferrocene-based chromophores with TCF-type acceptors (TCF = 2-dicyanomethylene-3-cyano-4-methyl-2,5-dihydrofuran) have been studied by using the ZINDO-SOS method. The results have revealed that OPA and TPA of ferrocenyl derivatives are affected by the strength of the acceptor, especially the pi-bridge conjugation length. The TPA cross section increases with increasing acceptor strength and pi-bridge conjugation length. The TCF-type acceptor with a phenyl group can lead to a larger TPA cross section. Quadrupole molecules have the largest TPA cross sections (2000-3000 GM), which are about 4 times that of the corresponding dipolar molecules, indicating larger interactions between the top and bottom branches. Finally, the origins of the two-photon excitations for ferrocenyl derivatives are analyzed. The calculations show that ferrocenyl derivatives with TCF-type acceptors (especially quadrupole molecules) are promising candidates for TPA materials.
采用ZINDO-SOS方法研究了一系列具有TCF型受体（TCF = 2-二氰基亚甲基-3-氰基-4-甲基-2,5-二氢呋喃）的二茂铁基发色团的电子结构、单光子吸收（OPA）和双光子吸收（TPA）性质。结果表明，二茂铁基衍生物的OPA和TPA受受体强度的影响，特别是π-桥共轭长度。TPA截面随受体强度和π-桥共轭长度的增加而增大。带有苯基的TCF型受体可导致更大的TPA截面。四极分子具有最大的TPA截面（2000 - 3000 GM），约为相应偶极分子的4倍，表明上下支之间的相互作用更大。最后，分析了二茂铁基衍生物双光子激发的起源。计算表明，具有TCF型受体的二茂铁基衍生物（特别是四极分子）是TPA材料的有前途的候选者。
