Inducing And Regulating Of Supramolecular Chirality Of Perylenebisimide Aggregates

Supramolecular chirality reflects the asymmetric stereochemical structure of supramolecular assemblies that constructed by intermolecular non-covalent interactions(such as electrostatic interaction,hydrogen bonding,π-π stacking,and metal coordination).The construction of functional supramolecular aggregates are important means of induction,regu lation and amplification of supramolecular chirality.Based on the host-guest-induced aggregation,chemical sensing with high selectivity and sensitivity and understanding of the origin of chirality can be realized through the induction and regulation of supramolecular chirality.Perylenebisimide dyes are a kind of well-developed building blocks and signal reporters of chiral-induced supramolecular aggregates since theirs excellent physical and chemical properties,and applications of PBIs in identfication sensing,optical catalysis,and biological fluorescent probes.In this thesis,perylenebisimide derivatives were employed as building blocks to construct supramolecular chiral aggregates through multiple non-covalent interactions.In a ternary mixed system,the induction and amplification of supramolecular chirality was realized,and applied to detect the Ag+.Furthermore,introducing meso-DACH into the chiral-induced supramolecular aggregates reached the chiral regulation and in-depth exploration of the formation process and mechanism of the anti-S-shaped CD-ee dependence.The thesis is divided into three chapters.The first chapter is preface.Firstly,the fundamental properties of Ag+…Ag+interaction and related researchs of Ag+-thiol coordination polymers are introduced;secondly,the characteristics,research progress and applications of perylenebisimide aggregates based on multiple non-covalent interactions are described;and finally,the research progress of supramolecular chirality and its expression are summarized.Chapter 2.Reports the design and synthesis of peryleneimide derivatives with terminal alkyl carboxylic acid groups,and building of a ternary mixed aggregates of PDIEtA,L-CysOEt and Ag+via cooperative of non-covalent interactions.Inducing perylenebisimides orderly assemble to supramolecular aggregates,via the formation of Ag+-CysOEt coordination polymers,leading to the expression and amplification of supramolecular chirality.The characteristic CD spectral singal at long wavelengths of the multi-component supramolecular polymers is applied for selective detection of Ag+.Chapter 3.Reports that supramolecular aggregates can be constructed following electrostatic interaction between achiral perylenebisimide derivative PDIEtA and chiral cyclohexanediamine DACH.The introduction of meso-DACH into the inducedchiral aggregates successfully realized the regulation of supramolecular chriality,that the S-shaped CD-ee dependence turns to anti-S-shaped.Interestingly,the "Sergeant and Soldiers" experiments reveal a supramolecular chrial amplification of S-shaped dependence.On the basis of the concentration effect of the "majority rules effect"experiments,it is speculated that the cooperative functions of both meso-and racDACH are responsible.The discovery of the anti-S-shaped CD-ee dependence helps understanding of the supramolecular chirality and provides a protocol for development of new supramolecular systems exhibiting the negative nonlinear CD-ee dependence.