Huilan Zhang , Michael Ho-Yeung Chan , Jonathan Lam , Ming-Yi Leung , Lixin Wu , 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 , Vivian Wing-Wah Yam","doi":"10.1039/d4qo02258k","DOIUrl":null,"url":null,"abstract":"<div><div>A new class of water-soluble amphiphilic Schiff base-containing platinum(<span>ii</span>) 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(<span>ii</span>) 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(<span>ii</span>) 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.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"12 6","pages":"Pages 1733-1747"},"PeriodicalIF":0.0000,"publicationDate":"2025-01-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Organic chemistry frontiers : an international journal of organic chemistry","FirstCategoryId":"1085","ListUrlMain":"https://www.sciencedirect.com/org/science/article/pii/S2052412925000440","RegionNum":0,"RegionCategory":null,"ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"","JCRName":"","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.