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钴(II)和镍(II)的己二酸导向自修复超分子金属凝胶:基于三阶光学非线性的比较光学现象的有趣支架

Adipic acid directed self-healable supramolecular metallogels of Co(II) and Ni(II): intriguing scaffolds for comparative optical-phenomenon in terms of third-order optical non-linearity.

作者信息

Lepcha Gerald, Singha Tara, Majumdar Santanu, Pradhan Amit Kumar, Das Krishna Sundar, Datta Prasanta Kumar, Dey Biswajit

机构信息

Department of Chemistry, Visva-Bharati University, Santiniketan 731235, India.

Department of Physics, Indian Institute of Technology Kharagpur, Kharagpur-721302, India.

出版信息

Dalton Trans. 2022 Sep 13;51(35):13435-13443. doi: 10.1039/d2dt01983c.

Abstract

Two brilliant outcomes of supramolecular self-assembly directed, low molecular weight organic gelator based self-healable Co(II) and Ni(II) metallogels were achieved. Adipic acid as the low molecular weight organic gelator and dimethylformamide (DMF) solvent are employed for the metallogelation process. Rheological analyses of both gel-scaffolds reveal mechanical toughness as well as visco-elasticity. Thixotropic behaviours of both the gels were scrutinized. Morphological variations due to the presence of two different metal ions with diverse metal-ligand coordinating interactions were established. The mechanistic pathways for forming stable metallogels of Co(II)-adipic acid (Co-AA) and Ni(II)-adipic acid (Ni-AA) were judiciously developed through infrared absorption spectral analysis. The nonlinear optical properties, such as the third-order process, of these synthesized metallogels were scrutinized by means of the -scan method at a beam excitation wavelength of 750 nm by a femtosecond laser with different excitation intensities ranging from 64 to 140 GW cm. The third-order nonlinear optical susceptibility () of the order of 10 esu was obtained from the measured -scan data. Both the metallogels exhibit positive nonlinear refraction and reverse saturable (RSA) absorption at high-intensity excitation. Co(II) and Ni(II) metallogels show nonlinear refractive indices () of (3.619 ± 0.146) × 10 cm GW and (3.472 ± 0.102) × 10 cm GW, respectively, and two photon absorption coefficients () of (1.503 ± 0.045) × 10 cm GW and (1.381 ± 0.029) × 10 cm GW at an excitation intensity of 140 GW cm. We also studied the optical limiting properties with a limiting threshold of 9.57 mJ cm. Therefore, both metallogels can be considered promising materials for photonic devices: for instance, for optical switching and optical limiting.

摘要

通过基于超分子自组装的低分子量有机凝胶剂,成功制备了具有自修复性能的Co(II)和Ni(II)金属凝胶,取得了两个显著成果。己二酸作为低分子量有机凝胶剂,二甲基甲酰胺(DMF)作为溶剂用于金属凝胶化过程。对两种凝胶支架进行流变学分析,结果表明它们具有机械韧性和粘弹性。对两种凝胶的触变行为进行了研究。确定了由于存在两种具有不同金属-配体配位相互作用的金属离子而导致的形态变化。通过红外吸收光谱分析,合理地推导了Co(II)-己二酸(Co-AA)和Ni(II)-己二酸(Ni-AA)形成稳定金属凝胶的机理途径。利用飞秒激光在750 nm的光束激发波长下,通过z扫描方法,在64至140 GW cm的不同激发强度下,对这些合成金属凝胶的非线性光学性质,如三阶过程进行了研究。从测量的z扫描数据中获得了10 esu量级的三阶非线性光学极化率()。两种金属凝胶在高强度激发下均表现出正非线性折射和反饱和(RSA)吸收。Co(II)和Ni(II)金属凝胶的非线性折射率()分别为(3.619 ± 0.146) × 10 cm GW和(3.472 ± 0.102) × 10 cm GW,在140 GW cm的激发强度下,双光子吸收系数()分别为(1.503 ± 0.045) × 10 cm GW和(1.381 ± 0.029) × 10 cm GW。我们还研究了光学限幅特性,其限幅阈值为9.57 mJ cm。因此,两种金属凝胶都可被视为光子器件的有前途的材料:例如,用于光开关和光学限幅。

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