Luminescene And Supramolecular Chirality Of Ag~+ Coordination Polymers With Chiral Thiol

Chirality is a ubiquitous phenomenon in nature.With the development of supramolecular chemistry,supramolecular chirality has become hotspots in the field of chemistry,which closely related to bionics,asymmetric catalysis and chiral advanced materials.In recent years,the non-covalent metallophilic interactions have increasingly attracted attention.Metal coordination polymers facilitated by the metallophilic interactions exhibit diverse photophysical and photochemical properties.Our group has reported a series of Ag(?)-SR metal coordination polymers involving Ag(?)-Ag(?)interaction in situ formed upon mixing the thiol ligand and Ag~+,and applied them for chiral recognition and sensing.Inspired by the preliminary work of our group,a series of thiol ligands were designed and synthesized in this dissertation,which aims to regulate the supramolecular chiral of the coordination polymers of these thiol ligands with Ag(?).In the meantime,the influence of the substituent in the thiol ligand on the phenyl ring of the acyl benzamide moiety and the interaction between side chains of the ligand moleculars on the spectroscopic properties and morphology of the coordination polymers were investigated.This dissertation consists of four chaptersChapter 1 introduces the characteristics and mechanism of metal-metal interaction.The general modes of Ag(?)-Ag(?)interactions were presented briefly.The formation and influencing factors of the metal coordination polymers were elaborated.The formation of chiral supramolecular polymers and the chirality inversion of chiral supramolecular polymers were next discussed.Finally,the research objectives of this dissertation are presented.Chapter 2 describes the synthesis and structure identification of two series of thiol ligand moleculars involved in this dissertation.In Chapter 3,it is primarily introduced that the hydrogen bonding between the side chains plays an important role in maintaining Ag(?)-L-NACAH metal coordination polymers.It was shown that the luminescent properties and chirality of the supramolecular metal coordination polymers can be regulated by the substituents at the phenyl ring of the acyl benzamide moiety.Infrared and fluorescence spectroscopy experiments confirmed the existence of hydrogen bonding between the side chains in the Ag(?)-L-NACAX polymers.This provides a new avenue for studying the spectral response mechanism of metal coordination polymers at the molecular level and for the regulation of chirality of supramolecular polymers.Chapter 4 reported an N-amidothiourea containing ?-turn structure and its aggregation.A thiol group and a luminescent pyrenyl group were introduced to generate PyPhe.The self-assembly and induced-assembly of PyPhe exhibited different spectral characteristics and structural properties.This research showed that the aggregation of PyPhe can be regulated by solvent composition and temperature.The aggregates formed from this mode have helical structure and showed racemate-rles effect in their chirality.PyPhe can also form metal coordination polymers with Ag(?),controlled by the Ag(I)-Ag(?)interaction.The spectral responses associated with Ag(?)-Ag(?)interactions were observed,from which the binding ratio of Ag(?)and PyPhe was found to be 1:1.Chiral amplification was observed in this aggregation mode.The study of this system is significant for designing functional supramolecular aggregates with different assembly modes.