Photoresponsive Halogen-Bonded Complexes of 1,3,5-Trifluoro-2,4,6-triiodobenzene and Alkoxyazopyridine Derivatives Based on Py-N···I Interactions: Synthesis, Structural, and Theoretical Insights

IF 3.2 2区化学 Q2 CHEMISTRY, MULTIDISCIPLINARY

Crystal Growth & Design Pub Date : 2024-11-05 DOI:10.1021/acs.cgd.4c0078110.1021/acs.cgd.4c00781

Jyoti Swarup Thakur, Omkar Dash, Kapil S. Ingle, Komal B. Lahoti, Athul Sudheendranath, Nagesh A. Bhale, Amol G. Dikundwar and Susanta K. Nayak*,

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Abstract

A series of (E)-4-((4-alkoxyphenyl)diazenyl)pyridine (AZ-n) derivatives were synthesized with varying alkoxy spacers (n = 8, 9, and 10), and their halogen-bonded complexes were obtained with 1,3,5-trifluoro-2,4,6-triiodobenzene in different stoichiometric ratios, which were further characterized by Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), single-crystal X-ray diffraction (SC-XRD), and powder X-ray diffraction (P-XRD) techniques. The structural analysis revealed the presence of Py-N···I halogen bond (XB) interactions in the complexes, resulting in a bent-shaped architecture rather than a star-shaped one. Hirshfeld surface analysis revealed the contribution of XB along different intermolecular interactions in the crystal packing. Computational analyses such as noncovalent index (NCI), quantum theory of atoms in molecules (QTAIM), electron localization function (ELF), and natural bond orbital (NBO) were carried out to understand the nature, strength, and electronic characteristics of XBs in these complexes. Further, these XB complexes show excellent photoresponsive behavior upon UV illumination, introducing a new range of supramolecular photoresponsive materials self-assembled by halogen bonding, thereby broadening the scope of potential applications within their respective systems.

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基于 Py-N-I 相互作用的 1,3,5-三氟-2,4,6-三碘苯和烷氧基氮吡啶衍生物的光致发光卤键配合物：合成、结构和理论见解

合成了一系列具有不同烷氧基间隔（n = 8、9 和 10）的 (E)-4-((4- 烷氧基苯基)偶氮)吡啶 (AZ-n) 衍生物，并以不同的化学计量比获得了它们与 1,3,5-三氟-2,4,6-三碘苯的卤键配合物、通过傅立叶变换红外光谱（FTIR）、差示扫描量热法（DSC）、单晶 X 射线衍射（SC-XRD）和粉末 X 射线衍射（P-XRD）技术对其进行了进一步表征。结构分析表明，复合物中存在 Py-N-I 卤素键 (XB) 相互作用，从而形成了弯形结构而非星形结构。Hirshfeld 表面分析揭示了 XB 在晶体堆积中沿着不同的分子间相互作用所起的作用。为了了解这些复合物中 XB 的性质、强度和电子特性，还进行了非共价指数（NCI）、分子中原子量子理论（QTAIM）、电子定位功能（ELF）和天然键轨道（NBO）等计算分析。此外，这些 XB 复合物在紫外光照射下表现出优异的光致抗蚀性，为通过卤素键自组装的超分子光致抗蚀性材料引入了一个新的范围，从而拓宽了它们在各自体系中的潜在应用范围。

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来源期刊

Crystal Growth & Design 化学-材料科学：综合

CiteScore

6.30

自引率

10.50%

发文量

650

审稿时长

1.9 months

期刊介绍： The aim of Crystal Growth & Design is to stimulate crossfertilization of knowledge among scientists and engineers working in the fields of crystal growth, crystal engineering, and the industrial application of crystalline materials. Crystal Growth & Design publishes theoretical and experimental studies of the physical, chemical, and biological phenomena and processes related to the design, growth, and application of crystalline materials. Synergistic approaches originating from different disciplines and technologies and integrating the fields of crystal growth, crystal engineering, intermolecular interactions, and industrial application are encouraged.