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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Thiophene-based terpyridine and its zinc halide complexes: third-order nonlinear optical properties in the near-infrared region
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Thiophene-based terpyridine and its zinc halide complexes: third-order nonlinear optical properties in the near-infrared region

机译：噻吩基吡啶及其卤化锌配合物：近红外区域的三阶非线性光学性质

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摘要

A novel 4'-(4-(diphenylamino) thienyl)-2,2':6',2 ''-terpyridine ligand (L) based on thiophene and its LZnX2 complexes (X = Cl, Br, I, SCN) was designed, synthesized and characterized by elemental analysis, far-IR, MALDI-TOF-MS, and single crystal X-ray diffraction analysis. Structural studies revealed that the central zinc(II) atom adopted a distorted trigonal bipyramidal coordination model. However, there were different hydrogen bonds and stacking models with different counter anions in the crystals. The absorption properties of the compounds were investigated with the aid of TD-DFT computational methods. Furthermore, the third-order nonlinear optical (NLO) properties were systematically studied via open-aperture Z-scan methods using a tunable wavelength femtosecond laser. The results from photophysical property investigations suggested that the complexation of the thiophene-based terpyridine ligand with zinc halides resulted in strong ICT/LLCT bands of about 450 nm, and the complexes exhibited strong nonlinear optical response in the near-infrared range around 850 nm. Above all, the two-photon absorption (2PA) cross-section values (sigma) were enhanced by coordination with zinc and influenced by halide ions, reaching up to 2583 GM (X = Br).
机译：基于噻吩及其LZnX2配合物（X = Cl，Br，I，SCN）的新型4'-（4-（二苯氨基）噻吩基）-2,2'：6'，2''-吡啶吡啶配体（L）为通过元素分析，远红外，MALDI-TOF-MS和单晶X射线衍射分析设计，合成和表征。结构研究表明，中心的锌（II）原子采用了扭曲的三角双锥体配位模型。但是，晶体中存在不同的氢键和具有不同抗衡阴离子的堆积模型。借助TD-DFT计算方法研究了化合物的吸收性能。此外，使用可调波长飞秒激光通过开孔Z扫描方法系统地研究了三阶非线性光学（NLO）特性。光物理性质研究的结果表明，基于噻吩的三联吡啶配体与卤化锌的络合产生约450 nm的强ICT / LLCT带，并且该络合物在约850 nm的近红外范围内表现出较强的非线性光学响应。最重要的是，通过与锌的配位并受卤离子的影响，双光子吸收（2PA）截面值（sigma）得以提高，达到2583 GM（X = Br）。

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