Dini Danilo, Hanack Michael, Egelhaaf Hans-Joachim, Sancho-García Juan Carlos, Cornil Jerome
Institutes of Organic Chemistry and Physical and Theoretical Chemistry, University of Tübingen, Auf der Morgenstelle 18, D 72076 Tübingen, Germany.
J Phys Chem B. 2005 Mar 31;109(12):5425-32. doi: 10.1021/jp048752t.
The synthesis, characterization, and various photophysical properties of axially substituted tetrapyrazinotetraazaporphyrinatotitanium(IV) oxide (Pyz(4)TAPTiO) (1), tetrapyrazinotetraazaporphyrinatovanadium(IV) oxide (Pyz(4)TAPVO) (2), tetrapyrazinotetraazaporphyrinatozirconium(IV) dihydroxide [Pyz(4)TAPZr(OH)(2)] (3) are reported. Nonlinear optical (NLO) properties of Pyz(4)TAPs 1-3 have been evaluated at 532 nm with nanosecond pulses for optical limiting (OL). It is found that the introduction of nitrogen atoms in the condensed rings of the tetrapyrrolic macrocycles together with the presence of axial substituents lead to an improvement of the excited-state absorption properties in comparison to phthalocyanines (Pcs). In the linear optical regime Pyz(4)TAPs 1-3 display a blue shift (about 50-60 nm) of the main UV-vis absorption bands with respect to Pcs and exhibit orange-red fluorescence, which can be observed with the eye in the case of 1. Frontier electronic orbitals of a Pyz(4)TAP could be depicted from available experimental data and the results of density functional theory (DFT) calculations. In the solid state, Pyz(4)TAPTiO (1) displays photoconducting properties.
报道了轴向取代的四吡嗪并四氮杂卟啉二氧化钛（IV）（Pyz(4)TAPTiO）（1）、四吡嗪并四氮杂卟啉二氧化钒（IV）（Pyz(4)TAPVO）（2）、四吡嗪并四氮杂卟啉二氢氧化锆（IV）[Pyz(4)TAPZr(OH)(2)]（3）的合成、表征及各种光物理性质。利用纳秒脉冲在532 nm下对Pyz(4)TAPs 1 - 3的非线性光学（NLO）性质进行了光限幅（OL）评估。研究发现，与酞菁（Pcs）相比，四吡咯大环稠环中氮原子的引入以及轴向取代基的存在导致激发态吸收性质得到改善。在线性光学区域，Pyz(4)TAPs 1 - 3的主要紫外 - 可见吸收带相对于Pcs出现蓝移（约50 - 60 nm），并呈现橙红色荧光，其中1的橙红色荧光肉眼可见。可根据现有实验数据和密度泛函理论（DFT）计算结果描绘Pyz(4)TAP的前沿电子轨道。在固态下，Pyz(4)TAPTiO（1）表现出光电导性质。
