{"title":"从宏观流变学特征解码金属超分子聚合物网络中的配位几何强化","authors":"Mostafa Ahmadi, Albert Poater, Sebastian Seiffert","doi":"10.1021/acs.macromol.4c01380","DOIUrl":null,"url":null,"abstract":"The control over coordination geometry in metallo-supramolecular polymer networks not only helps developing new polymer structures but also provides new measures of metal complex characteristics. Herein, we compare multiscale characteristics of networks obtained by homo- and heteroleptic association of mono-, bi-, and tridentate ligands, as reflected in rheological measurements and DFT calculations. Accordingly, tetra-arm poly(ethylene glycol) (tetraPEG), functionalized with pyridine, phenanthroline, and terpyridine, form parent homoleptic networks, while their combination with a tetraPEG functionalized by the sterically demanding dimesitylene substituted phenanthroline forms heteroleptic networks. Among all employed transition metal ions, only Cu<sup>+/2+</sup> and Pd<sup>2+</sup> comply with the coordination geometry necessities of all parent and mixed networks, ranging from trigonal to octahedral, providing good candidates for wide network topology rearrangements. Our rheological measurements and DFT calculations demonstrate that the stability of homoleptic complexes depends primarily on metal identity, whereas that of heteroleptic equivalents increases with increasing the denticity of the slim ligand, being a complex function of steric, electronic, and π–π interactions.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":null,"pages":null},"PeriodicalIF":5.1000,"publicationDate":"2024-09-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Decoding Coordination Geometry Enforcement in Metallo-supramolecular Polymer Networks from Macroscopic Rheological Signatures\",\"authors\":\"Mostafa Ahmadi, Albert Poater, Sebastian Seiffert\",\"doi\":\"10.1021/acs.macromol.4c01380\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"The control over coordination geometry in metallo-supramolecular polymer networks not only helps developing new polymer structures but also provides new measures of metal complex characteristics. Herein, we compare multiscale characteristics of networks obtained by homo- and heteroleptic association of mono-, bi-, and tridentate ligands, as reflected in rheological measurements and DFT calculations. Accordingly, tetra-arm poly(ethylene glycol) (tetraPEG), functionalized with pyridine, phenanthroline, and terpyridine, form parent homoleptic networks, while their combination with a tetraPEG functionalized by the sterically demanding dimesitylene substituted phenanthroline forms heteroleptic networks. Among all employed transition metal ions, only Cu<sup>+/2+</sup> and Pd<sup>2+</sup> comply with the coordination geometry necessities of all parent and mixed networks, ranging from trigonal to octahedral, providing good candidates for wide network topology rearrangements. Our rheological measurements and DFT calculations demonstrate that the stability of homoleptic complexes depends primarily on metal identity, whereas that of heteroleptic equivalents increases with increasing the denticity of the slim ligand, being a complex function of steric, electronic, and π–π interactions.\",\"PeriodicalId\":51,\"journal\":{\"name\":\"Macromolecules\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":5.1000,\"publicationDate\":\"2024-09-11\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Macromolecules\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://doi.org/10.1021/acs.macromol.4c01380\",\"RegionNum\":1,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"POLYMER SCIENCE\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Macromolecules","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1021/acs.macromol.4c01380","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"POLYMER SCIENCE","Score":null,"Total":0}
Decoding Coordination Geometry Enforcement in Metallo-supramolecular Polymer Networks from Macroscopic Rheological Signatures
The control over coordination geometry in metallo-supramolecular polymer networks not only helps developing new polymer structures but also provides new measures of metal complex characteristics. Herein, we compare multiscale characteristics of networks obtained by homo- and heteroleptic association of mono-, bi-, and tridentate ligands, as reflected in rheological measurements and DFT calculations. Accordingly, tetra-arm poly(ethylene glycol) (tetraPEG), functionalized with pyridine, phenanthroline, and terpyridine, form parent homoleptic networks, while their combination with a tetraPEG functionalized by the sterically demanding dimesitylene substituted phenanthroline forms heteroleptic networks. Among all employed transition metal ions, only Cu+/2+ and Pd2+ comply with the coordination geometry necessities of all parent and mixed networks, ranging from trigonal to octahedral, providing good candidates for wide network topology rearrangements. Our rheological measurements and DFT calculations demonstrate that the stability of homoleptic complexes depends primarily on metal identity, whereas that of heteroleptic equivalents increases with increasing the denticity of the slim ligand, being a complex function of steric, electronic, and π–π interactions.
期刊介绍:
Macromolecules publishes original, fundamental, and impactful research on all aspects of polymer science. Topics of interest include synthesis (e.g., controlled polymerizations, polymerization catalysis, post polymerization modification, new monomer structures and polymer architectures, and polymerization mechanisms/kinetics analysis); phase behavior, thermodynamics, dynamic, and ordering/disordering phenomena (e.g., self-assembly, gelation, crystallization, solution/melt/solid-state characteristics); structure and properties (e.g., mechanical and rheological properties, surface/interfacial characteristics, electronic and transport properties); new state of the art characterization (e.g., spectroscopy, scattering, microscopy, rheology), simulation (e.g., Monte Carlo, molecular dynamics, multi-scale/coarse-grained modeling), and theoretical methods. Renewable/sustainable polymers, polymer networks, responsive polymers, electro-, magneto- and opto-active macromolecules, inorganic polymers, charge-transporting polymers (ion-containing, semiconducting, and conducting), nanostructured polymers, and polymer composites are also of interest. Typical papers published in Macromolecules showcase important and innovative concepts, experimental methods/observations, and theoretical/computational approaches that demonstrate a fundamental advance in the understanding of polymers.