Construction And Fluorescent Sensing Properties Of Supramolecular Fluorescent Materials Based On Multipod-pillar[5]arene And Amides

In recent years,the supramolecular fluorescence materials received widespread attention because of its abundant applications.In supramolecular fluorescence materials,the noncovalent-bond-based self-assembly gives these kind materials reversible stimulus response and control performance for outer stimulus.Therefore,supramolecular fluorescence materials show excellent prospect in the smart materials.Based on summary literatures,this thesis introduces the construction of supramolecular fluorescence materials based on small molecules and pillar[n]arenes,other macrocyclic compounds and the pillar[n]arenes-based of supramolecular fluorescence materials in sensing,cell imaging and other fields of research progress.In order to develop novel and efficient fluorescent materials and improve the selectivity and sensitivity of them,this thesis designed three kind supramolecular fluorescence materials,and the fluorescent sensing as well as heavy metal ions separation properties of these materials have been investigated as following three parts:The first part,a novel functionalized tripod-pillar[5]arene（TP5）was synthesized through benzene-1,3,5-tricarbonyl trichloride and diethyl benzene amine acetyl sulfide functionalized pillar[5]arene.Then,amphipathic dipode-piperazine guest（APBr）was synthesized through p-hydroxybenzaldehyde functionalized quaternary amine salt and3,3’-（piperazine-1,4-diyl）bis（propan-1-amine）.TP5 and APBr was assembled in DMSO/H₂O through host-guest interactions to form TP5-APBr supramolecular nanoparticles.After adding S^2-to the TP5-APBr,the nanoparticles were transformed into nanorods.With continue adding the Pb²⁺,PbS fluorescent nanoparticle insitu generated by the inducement of Pb²⁺.The obtained PbS fluorescent nanoparticles have strong fluorescence emission at 476 nm,adding other ions could not induce similar response.Therefore,TP5-APBr-S^2-could sense Pb²⁺with specific selectivity.This research not only provides a new method for the preparation of PbS fluorescent nanoparticles,but also broadens the application field of supramolecular fluorescent materials.The second part,tripod-pyridine amide compound（G）was synthesized through benzene-1,3,5-tricarbonyl trichloride and aminopyridine.Then,tripod-benzimidazole compounds（TBCN）were synthesized using trimeric acid and o-phenylenediamine.G and TBCN was assembled as supramolecular gel TBG through multipod synergistic effect in DMSO/H₂O.Supramolecular gel TBG shows white light and AIE effect.The research results of metal ion recognition indicated that TBG could detect Fe³⁺with highly selectivity.At the same time,after adding Fe³⁺to TBG,the obtained metal organic gel TBG-Fe could respond H₂PO₄^-with specific selectivity and highly sensitivity.Moreover,the dry gel powder of TBG could adsorb Fe³⁺with highly efficiency,the adsorption rate reached 99%.In addition,the gel film based on TBG and TBG-Fe could easily and quickly detect Fe³⁺and H₂PO₄^-.This research provides an effective idea for the design of intelligent stimulus response white light materials and the detection of multiple analytes.The third part,the naphthalene imide fluorescent sensors（NTCY）with tetrapod-pyridine di-hydrazide was synthesized.In the fluorescent sensors S-NTCY,naphthalene imide act as fluorescent group andπ-πstacking group,tetrapod-pyridine di-hydrazide act as assembly site and coordination site.In S-NTCY could selectively fluorescent“turn-on”response Hg²⁺with highly sensivity.The mechanism research showed that S-NTCY and Hg²⁺may form coordination supramolecular polymer.This work provides a feasible direction for design of the fluorescent sensors for simultaneous detection and removal of heavy metal ions.In conclusion,this thesis designed and synthesized supramolecular fluorescent materials based-on multipod structure to supply selective and sensitive binding for target guests.These supramolecular fluorescent materials could simultaneously detect and remove Pb²⁺,Hg²⁺,Fe³⁺.This thesis has certain research value and application prospects.