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

IF 5.3 2区化学 Q2 CHEMISTRY, PHYSICAL Journal of Molecular Liquids Pub Date : 2025-03-01 DOI:10.1016/j.molliq.2025.127268

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

{"title":"Solubility measurements and thermodynamic correlation of bis(imino)pyridine-based Cu and Ni complexes in pure solvents","authors":"Talha Baig , Ziyuan Pang , Mubashar Ilyas , Muhammad Abbas , Sheza Tahir , Xiaoli Ma","doi":"10.1016/j.molliq.2025.127268","DOIUrl":null,"url":null,"abstract":"<div><div>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.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"425 ","pages":"Article 127268"},"PeriodicalIF":5.3000,"publicationDate":"2025-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of Molecular Liquids","FirstCategoryId":"92","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S0167732225004350","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}

引用次数: 0

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.

查看原文

微信好友朋友圈 QQ好友复制链接

本刊更多论文

求助全文

约1分钟内获得全文去求助

IF 3.5 4区医学AutoimmunityPub Date : 2020-06-01 DOI: 10.1080/08916934.2020.1750011

Dan Li, Xiaoqing Li, Mingyue Duan, Yufeng Dou, Yuan Feng, Nan Nan, Wanggang Zhang

FRI0266 The mechanism of umbilical cord mesenchymal stem cells in the upregulation of regulatory t cells by tgf-b1 in systemic lupus erythematosus

IF 27.4 1区医学Annals of the Rheumatic DiseasesPub Date : 2013-06-01 DOI: 10.1136/annrheumdis-2013-eular.1393

L. Sun, Le Lu, D. Wang, X. Li

Umbilical Cord Mesenchymal Stem Cell Secretome: A Potential Regulator of B Cells in Systemic Lupus Erythematosus.

IF 5.6 2区生物学International Journal of Molecular SciencesPub Date : 2024-11-21 DOI: 10.3390/ijms252312515

Adelina Yordanova, Mariana Ivanova, Kalina Tumangelova-Yuzeir, Alexander Angelov, Stanimir Kyurkchiev, Kalina Belemezova, Ekaterina Kurteva, Dobroslav Kyurkchiev, Ekaterina Ivanova-Todorova

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.