Solubility measurements and thermodynamic correlation of bis(imino)pyridine-based Cu and Ni complexes in pure solvents

IF 5.2 2区化学 Q2 CHEMISTRY, PHYSICAL Journal of Molecular Liquids Pub Date : 2025-05-01 Epub Date: 2025-03-01 DOI:10.1016/j.molliq.2025.127268

Talha Baig , Ziyuan Pang , Mubashar Ilyas , Muhammad Abbas , Sheza Tahir , Xiaoli Ma

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Abstract

In this work, the solubility of a bis(imino)pyridine-based ligand L = 2,6-Bis[1-(cyclohexylimino)ethyl]pyridine and its two metal complexes LCuCl₂ and LNiCl₂ is measured by static equilibrium method in four selected solvents. These complexes are widely used in catalysis, polymerization, cycloaddition reactions, anticancer drugs, and in optoelectronic materials where the solvation process has a critical impact on their properties. The solubility data is vital for improving the crystallization process and the efficiency of homogeneous catalysis. Six thermodynamic models (Apelblat, Polynomial, Yaws, Vant’s Hoff, λh, and NRTL) are applied to analyze the solubility values of LH and four models (Apelblat, Polynomial, Yaws, Vant’s Hoff) are applied for both metal complexes LCuCl₂ and LNiCl₂. To ensure the precision of experimental data, the ARD and RMSD values are calculated for accuracy evaluation. The solubility data of L indicates that dichloromethane is the best reaction solvent having its highest solubility value 7.515 × 10² x at 298.15 K and absolute ethanol is the best solvent for its crystallization. Similarly, the solubility data collected for LCuCl₂ and LNiCl₂ reveals that trichloromethane is the best reaction solvent having highest solubility values 4.188 × 10³ x and 4.279 × 10³ x respectively at 298.15 K and acetone is the crystallization solvent for both of these metal complexes. The polynomial model represents the optimal choice for accurately fitting the solubility data related to all three examined compounds having average ARD values less than 1 %. Hirshfeld surface analysis show that H⋯H contacts are the most significant interactions, about 68.2 % in the compound LCuCl₂. Moreover, molecular electrostatic potential indicates that the N atom and the metal centers of the two compounds exhibit distinct electronegativity. In addition, functions related to apparent thermodynamics were obtained. The dissolution process proved endothermic and entropy rose in the experimental settings, with spontaneous energy accounting for the variation in solubility.

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双（亚胺）吡啶基Cu和Ni配合物在纯溶剂中的溶解度测量和热力学相关性

本文采用静态平衡法测定了双（亚氨基）吡啶基配体L = 2,6-双[1-（环己基）乙基]吡啶及其两种金属配合物LCuCl2和LNiCl2在四种选定溶剂中的溶解度。这些配合物广泛应用于催化、聚合、环加成反应、抗癌药物以及光电材料中，其中溶剂化过程对其性能有关键影响。溶解度数据对改善结晶过程和均相催化效率具有重要意义。采用Apelblat、Polynomial、Yaws、Vant’s Hoff、λh和NRTL 6种热力学模型分析LH的溶解度值，采用Apelblat、Polynomial、Yaws、Vant’s Hoff 4种模型分析LCuCl2和LNiCl2的金属配合物。为了保证实验数据的精度，计算ARD和RMSD值进行精度评价。L的溶解度数据表明，在298.15 K下，二氯甲烷的溶解度最高，为7.515 × 102 x，二氯甲烷是L的最佳反应溶剂，无水乙醇是L的最佳结晶溶剂。同样，LCuCl2和LNiCl2的溶解度数据表明，在298.15 K下，三氯甲烷的溶解度最高，分别为4.188 × 103 x和4.279 × 103 x，而丙酮是这两种金属配合物的结晶溶剂。多项式模型代表了准确拟合与所有三种平均ARD值小于1%的被测化合物相关的溶解度数据的最佳选择。Hirshfeld表面分析表明，H⋯H接触是最重要的相互作用，在化合物LCuCl2中约占68.2%。此外，分子静电势表明，两种化合物的N原子和金属中心表现出明显的电负性。此外，还得到了与表观热力学相关的函数。溶解过程被证明是吸热的，在实验环境下熵增加，自发能解释溶解度的变化。

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来源期刊

Journal of Molecular Liquids 化学-物理：原子、分子和化学物理

CiteScore

10.30

自引率

16.70%

发文量

2597

审稿时长

78 days

期刊介绍： The journal includes papers in the following areas: – Simple organic liquids and mixtures – Ionic liquids – Surfactant solutions (including micelles and vesicles) and liquid interfaces – Colloidal solutions and nanoparticles – Thermotropic and lyotropic liquid crystals – Ferrofluids – Water, aqueous solutions and other hydrogen-bonded liquids – Lubricants, polymer solutions and melts – Molten metals and salts – Phase transitions and critical phenomena in liquids and confined fluids – Self assembly in complex liquids.– Biomolecules in solution The emphasis is on the molecular (or microscopic) understanding of particular liquids or liquid systems, especially concerning structure, dynamics and intermolecular forces. The experimental techniques used may include: – Conventional spectroscopy (mid-IR and far-IR, Raman, NMR, etc.) – Non-linear optics and time resolved spectroscopy (psec, fsec, asec, ISRS, etc.) – Light scattering (Rayleigh, Brillouin, PCS, etc.) – Dielectric relaxation – X-ray and neutron scattering and diffraction. Experimental studies, computer simulations (MD or MC) and analytical theory will be considered for publication; papers just reporting experimental results that do not contribute to the understanding of the fundamentals of molecular and ionic liquids will not be accepted. Only papers of a non-routine nature and advancing the field will be considered for publication.