Zhou Xin, Ren Ai-Min, Feng Ji-Kang
State Key Laboratory of Theoretical and Computational Chemistry, Institute of Theoretical Chemistry, Jilin University, Changchun 130023, China.
Chemistry. 2004 Nov 5;10(22):5623-31. doi: 10.1002/chem.200400251.
We have theoretically investigated a series of butadiyne-linked porphyrin derivatives that exhibit large two-photon absorption (TPA) cross sections in the visible-IR range. The electronic structure, one-photon absorption (OPA), and TPA properties have been studied in detail. We found that the introduction of a butadiyne linkage and the increase of the molecular dimensionality from monomer to dimer determine the OPA intensities of Q band and Soret band, respectively. A most important role for the enhancement of the TPA cross section is played by introducing a butadiyne bridge. The complementary coordination and the combination of the terminal free base and the core zinc porphyrin are also two effective factors for the enhancement of the TPA efficiency. The dimer with two porphyrins linked at meso-positions by a butadiyne linkage results in a maximum TPA cross section (79.35 x 10(-48) cm4 s per photon). Our theoretical findings are consistent with the recent experimental observations. This series of porphyrin derivatives as promising TPA materials are the subject of further investigation.
我们从理论上研究了一系列在可见-红外范围内表现出大双光子吸收（TPA）截面的丁二炔连接的卟啉衍生物。详细研究了其电子结构、单光子吸收（OPA）和TPA性质。我们发现，丁二炔连接的引入以及分子维度从单体到二聚体的增加分别决定了Q带和Soret带的OPA强度。引入丁二炔桥对增强TPA截面起着最重要的作用。末端游离碱与核心锌卟啉的互补配位以及二者的结合也是提高TPA效率的两个有效因素。通过丁二炔连接在中位连接两个卟啉的二聚体产生了最大的TPA截面（每光子79.35×10(-48) cm4 s）。我们的理论发现与最近的实验观察结果一致。这一系列卟啉衍生物作为有前景的TPA材料有待进一步研究。
