Huilan Zhang, Michael Ho-Yeung Chan, Jonathan Lam, Ming-Yi Leung, Lixin Wu and Vivian Wing-Wah Yam
{"title":"Solvation and temperature-modulated supramolecular assembly of amphiphilic water-soluble Schiff base-containing platinum(ii) complexes†‡","authors":"Huilan Zhang, Michael Ho-Yeung Chan, Jonathan Lam, Ming-Yi Leung, Lixin Wu and Vivian Wing-Wah Yam","doi":"10.1039/D4QO02258K","DOIUrl":null,"url":null,"abstract":"<p >A new class of water-soluble amphiphilic Schiff base-containing platinum(<small>II</small>) complexes with dendritic triethylene glycol units has been investigated to show self-assembly properties by the balance of multiple noncovalent interactions including hydrophobic, intermolecular Pt⋯Pt and π–π stacking interactions in water or DMSO–water solutions, accompanied by drastic spectroscopic changes. The UV–vis spectra have been recorded, and the electronic structures and intermolecular Pt⋯Pt interactions have been confirmed by computational studies and non-covalent interaction (NCI) analysis of the dimer of the complex. These complexes have been found to exhibit a cooperative self-assembly mechanism, in which the molecules were stacked in a head-to-tail arrangement in a slightly staggered fashion. Additionally, the length of the alkoxy chains has been found to show a significant effect on the extent of Pt⋯Pt and π–π stacking interactions and the stability of their self-assembled aggregates. Under the influence of temperature, this class of Schiff base-containing platinum(<small>II</small>) complexes has been shown to exhibit an unexpected hysteresis effect and unusual thermo-responsive behavior accompanied by morphological transformation. This work represents a rare example of a systematic study on the self-assembly properties of water-soluble platinum(<small>II</small>) Schiff base complexes induced by molecular hydrophobicity, solvation and temperature. It provides an in-depth insight into the rational molecular design for the construction of supramolecular architectures and potential advances in stimuli-responsive probes.</p>","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":" 6","pages":" 1733-1747"},"PeriodicalIF":4.6000,"publicationDate":"2025-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Organic Chemistry Frontiers","FirstCategoryId":"92","ListUrlMain":"https://pubs.rsc.org/en/content/articlelanding/2025/qo/d4qo02258k","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, ORGANIC","Score":null,"Total":0}
引用次数: 0
Abstract
A new class of water-soluble amphiphilic Schiff base-containing platinum(II) complexes with dendritic triethylene glycol units has been investigated to show self-assembly properties by the balance of multiple noncovalent interactions including hydrophobic, intermolecular Pt⋯Pt and π–π stacking interactions in water or DMSO–water solutions, accompanied by drastic spectroscopic changes. The UV–vis spectra have been recorded, and the electronic structures and intermolecular Pt⋯Pt interactions have been confirmed by computational studies and non-covalent interaction (NCI) analysis of the dimer of the complex. These complexes have been found to exhibit a cooperative self-assembly mechanism, in which the molecules were stacked in a head-to-tail arrangement in a slightly staggered fashion. Additionally, the length of the alkoxy chains has been found to show a significant effect on the extent of Pt⋯Pt and π–π stacking interactions and the stability of their self-assembled aggregates. Under the influence of temperature, this class of Schiff base-containing platinum(II) complexes has been shown to exhibit an unexpected hysteresis effect and unusual thermo-responsive behavior accompanied by morphological transformation. This work represents a rare example of a systematic study on the self-assembly properties of water-soluble platinum(II) Schiff base complexes induced by molecular hydrophobicity, solvation and temperature. It provides an in-depth insight into the rational molecular design for the construction of supramolecular architectures and potential advances in stimuli-responsive probes.
期刊介绍:
Organic Chemistry Frontiers is an esteemed journal that publishes high-quality research across the field of organic chemistry. It places a significant emphasis on studies that contribute substantially to the field by introducing new or significantly improved protocols and methodologies. The journal covers a wide array of topics which include, but are not limited to, organic synthesis, the development of synthetic methodologies, catalysis, natural products, functional organic materials, supramolecular and macromolecular chemistry, as well as physical and computational organic chemistry.