Pt(?)-Pyridine Coordination Based 3D/2D Supramolecular Coordination Framework Materials In Assembly,Adsorption,Fluorescence,and Photocatalytic Properties Study

In the past decades,coordination self-assemblies based on metal ligand bonds with various configurations and functions have become one of the most attractive topics in supramolecular chemistry and materials science.The directivity and predictability of assemblies provide a definite size and shape for preparing discrete supramolecular coordination complexes(SCCs).Compared with metal organic frameworks(MOFs)that have the same metal ligand bonds,SCCs possess mild reaction conditions and simple preparation methods.However,SCCs lack periodicity,orderliness and porosity owing to their discreteness.In order to solve this problem,we combined the basic characteristics of SCCs and MOFs to propose a new concept?supramolecular coordination frameworks(SCFs).SCFs have the predesigned and well-defined shapes,highly ordered structure and simple preparation method.In this paper,the preparation method,structure design and performance of SCFs were discussesd in some detail.This paper consists of five parts:In chapter 1,the concept,structural characteristic and research significance of supramolecular coordination chemistry are summarized.Next,the structure design and research progress of Pt(?)-based SCCs are introduced in detail.The structural design and characteristic of MOFs are also described in detail.Finally,we integrate the basic characteristics of SCCs and MOFs,and proposed the research objective and specific experimental scheme in this paper.In chapter 2,a new concept,supramolecular coordination frameworks(SCFs)are proposed by combining the concepts of discrete SCCs and infinite MOFs in the first time.A diamondoid-liked SCF with infinite 3D structure was obtained by a stepwise induced synthesis method using a diamondoid-liked supramolecular coordination cage and 180°diplatinum(?)ligand.The structure and morphology were characterized and showed that these SCFs with nanometer size can achieve regular octahedral structure with controllable shape and highly ordered micron size by heating and evaporation in DMSO.This study demonstrates the potential application of SCFs in the precise construction of highly regulated porous framework.In chapter 3,on the basis of the second chapter,the preparation method of SCFs was further improved.Two Pt(?)-based diamondoid-liked SCFs materials with different sizes were prepared by one-pot synthesis method.The structure and property study shown that these SCFs possess well-defined periodicity and porosity.We performed rheological experiments for these SCFs and shown that these rigid SCFs can be directly converted to metallic gels at high concentration in DMSO.In addition,they can selectively adsorb and release anionic dyes and drugs in the aqueous environment.Therefore,the SCFs materials have potential applications in biological and medical fields,such as drug delivery.In chapter 4,based on the mature preparation methods of SCFs in the previous two chapters,the purpose of this chapter is to introduce different functional groups ligands into SCFs to enrich their application fields.Two novel 2D SCFs were constructed using tetrastyrene derivatives with fluorescent chromophore and 180°diplatinum(?)ligand.The fluorescence properties study shown that SCFs exhibited aggregation induced emission effect in aqueous phase,and they have been successfully used as fluorescent platforms and energy donors to fabricate efficient artificial light-harvesting materials with two fluorescent acceptors(Nile Red and Sulforhodamine 101)via noncovalent interactions in aqueous solution.Furthermore,these light-harvesting materials have been applied for promoting cancer cell imaging with a full shift of imaging channels from blue/green channels to the red channel.Therefore,these AIE and light-harvesting materials with a long excitation-emission gap and the single-channel/long-wavelength emission could offer super-resolution microscopy and fluorescence sensing in aqueous solution.In chapter 5,the porphyrin derivatives with photosensitive and 180°diplatinum(?)ligand were used to construct 2D SCFs.In addition,pyridine cation can inhibit the self-aggregation of porphyrin by the electrostatic repulsive interaction between layers,which can improve the efficiency of producing ¹O₂.The results indicated that SCFs can produce ¹O₂under 650 nm light.Therefore,this SCFs have potential application value in photodynamic therapy.