探索具有 (N,N,O)-供体配体及其铜 (II) 类似物的两种硝基镍 (II) 配合物的光开关特性,Inorganic Chemistry

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探索具有 (N,N,O)-供体配体及其铜 (II) 类似物的两种硝基镍 (II) 配合物的光开关特性
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2022-04-16 , DOI: 10.1021/acs.inorgchem.2c00526
Patryk Borowski ₁ , Sylwia E Kutniewska ₁ , Radosław Kamiński ₁ , Adam Krówczyński ₁ , Dominik Schaniel ₂ , Katarzyna N Jarzembska ₁

Affiliation

报道了两种可光切换的镍 (II) 硝基配位化合物及其铜 (II) 类似物。在所有这些系统中，金属中心被含有 2-吡啶甲胺或 8-氨基喹啉片段的 ( N , N , O )-供体配体螯合。使用晶体学和光谱技术辅以计算分析对所研究的化合物进行了深入研究。它们易于合成且稳定，所有化合物均发生硝基异构化反应。然而，铜和镍系统在其结构和可转换特性方面存在显着差异。根据固态红外光谱结果，400-660 nm 光照射基态 (η ² -O , O ')-κ-亚硝基铜 (II) 配合物在 10 K 时诱导相当温和的转化为亚稳键异构体，其仅在大约 60-80 K 时可见。反过来，在可见光照射下（约530 nm 激发波长），所检查的镍 (II) 配合物的基态硝基异构体转变为内硝基形式。对于两种镍 (II) 系统，可以实现约 35% 的转化率，并且在暴露于 LED 光 30-45 分钟后（晶体在更长的照射下衰减）后，在单晶的情况下确定在 160 K 时产生的晶体结构，如红外光谱结果所示，薄膜样品的转化率约为 95%。远藤的痕迹-硝基键异构体保持在 200-220 K，异构化反应被证明是完全可逆的。

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Exploring Photoswitchable Properties of Two Nitro Nickel(II) Complexes with (N,N,O)-Donor Ligands and Their Copper(II) Analogues

Two photoswitchable nickel(II) nitro coordination compounds and their copper(II) analogues are reported. In all these systems, the metal center is chelated by (N,N,O)-donor ligands containing either 2-picolylamine or 8-aminoquinoline fragments. The studied compounds were thoroughly investigated using crystallographic and spectroscopic techniques supplemented by computational analysis. They are easy to synthesize and stable, and all compounds undergo the nitro group isomerization reaction. Nevertheless, there are significant differences between the copper and nickel systems regarding their structural and switchable properties. According to the solid-state IR spectroscopy results, 400–660 nm light irradiation of the ground-state (η²-O,O′)-κ-nitrito copper(II) complexes at 10 K induces a rather moderate conversion to a metastable linkage isomer, which is visible only up to approximately 60–80 K. In turn, upon visible light irradiation (ca. 530 nm excitation wavelength), the ground-state nitro isomers of the examined nickel(II) complexes transform into the endo-nitrito forms. It was possible to achieve about 35% conversion for both nickel(II) systems and to determine the resulting crystal structures at 160 K in the case of single crystals after 30–45 min of exposure to LED light (crystals decayed with longer irradiation), and roughly 95% conversion was achieved for thin-film samples as indicated by the IR spectroscopy results. Traces of the endo-nitrito linkage isomers remained up to 200–220 K, and the isomerization reaction was proven to be fully reversible.

更新日期：2022-04-16

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