Construction And Luminescent Properties Of Supramolecular Organoplatinum(?)complexes Based On Coordination-driven Self-assembly

Non-covalent interactions are widespread in nature,such as the pairing of single-stranded NDA to form a DNA double helix structure and the folding of simple polypeptides into complex proteins.Supramolecular chemistry is inspired by natural biological systems,and has been committed to constructing complex supramolecular systems by simple molecules through non-covalent interactions.However,for the construction of multi-scale self-components with controllable shapes and functions,it is still challenging to choose a suitable protocol.Coordination-driven self-assembly provides a"bottom-up"method to construct supramolecular coordination complexes(SCCs),through strategies to spontaneously form metal-ligands between pre-designed metal acceptors and organic donors Bond to form a well-defined two-dimensional metal ring or three-dimensional metal cage.In addition,supramolecular coordination complexes usually show a well-defined inner cavity with adjustable size and shape,which is used in host-guest chemistry,catalysis,molecular reactors,supramolecular polymers,bioengineering,etc.Provides motivation.Although many metal complexes with attractive optical properties are known,the prospect of luminescent materials based on supramolecular coordination complex platforms as advanced optical materials is relatively underdeveloped.In this thesis,the classical aggregation-induced luminescence(AIE)molecule tetraphenylethylene(TPE)and the traditional aggregation-induced quenching(ACQ)molecule triphenylamine(TPA)are used as molecular building blocks,and the superstructure is constructed by the strategy of coordination-driven self-assembly.Molecular metal organic light emitting system.These supramolecular systems show good fluorescence emission in dilute solutions and aggregate states.This is a unique phenomenon that bridges the ACQ and AIE effects.The content of this paper mainly includes the following aspects:Chapter one,we reviews various supramolecular metal coordination self-assembly systems,self-assembled luminescent materials based on supramolecular metal coordination and related applications of supramolecular metal coordination luminescent materials,and finally puts forward the topic of this thesis.Chapter two,we designed and synthesized two tetraimidazole-based ligands with TPE group as the core skeleton.These two ligands construct two kinds of supramolecular metal-organic bicyclic structures with similar structures and different photophysical properties through coordination bond-directed self-assembly.The chemical composition of the obtained macrocycle was characterized in detail by the hydrogen spectrum and phosphorus spectrum of the multi-nuclear NMR technology,and the electrospray time-of-flight mass spectrometry,which proved that the system is a single,discrete double-triangular macrocyclic structure.Subsequent fluorescence spectra show that the two metal double rings with tiny structural differences have obvious differences in fluorescence behavior.Chapter three,we designed and synthesized two kinds of hexagonal metal rings,which are composed of different types of optically active units,triphenylamine(TPA)and tetraphenylethylene(TPE).Specifically,these metal macrocycles are assembled from alternating TPA-based bipyridine organic donors and TPE-based organoplatinum(?)acceptors,in which metal-ligand bonds are formed spontaneously.This special conformation gives the metal ring unique photophysical behavior,including strong luminescence in dilute solutions and high concentrations,controlling the fluorescence behavior by adjusting the polarity and solubility of different solvents,and improving the solid-state fluorescence quantum yield((37)_F).This work not only deepens people's understanding of the various fluorescent groups used to construct SCCs,but also enriches potential materials for fluorescent sensors and advanced optical devices.