Synthesis Of Bis(salamo)-Like Fluorescence Sensors And Study On The Photophysical Properties Of Their Metal Complexes

Two naphthalenediol-based symmetric bis?salamo?-type ligands H₄L¹ and H₄L² have been designed,and a 3d-4f complex and three 3d metal complexes were synthesized.The single crystal structure of the complexes were fully characterized by elemental analyses,FT-IR,UV-Visible spectroscopy,single crystal X-ray crystallography,and Hirshfeld surfaces analyses.Meanwhile,the fluorescent properties of the complexes have also been studied in depth.Complex 1:Empirical formula,C₃₆H₃₄Zn₂YN₄O₁₄,Formula weight,966.32,Triclinic,P-1,Unit call dimensions:a=1.25869?4?nm,b=1.32704?6?nm,c=1.56246?6?nm,?=114.271?4?°,?=105.128?3?°,?=99.290?3?°,Z=2,V=2.18702?17?nm³,R₁=0.0470,wR₂=0.1177;Complex 2:Ni₃?L???-OAc?₂?CH₃OH?₃]·CH₃OH·0.25CHCl₃ Empirical formula,C_38.25H_44.25Cl_0.75Ni₃N₆O₂₀,Formula weight,1110.76,Triclinic,P-1,Unit call dimensions:a=1.25099?7?nm,b=1.28563?7?nm,c=1.49822?8?nm,?=78.145?2?°,?=86.018?2?°,?=73.599?2?°,Z=2,V=2.2621?2?nm³,R₁=0.0489,wR₂=0.1329;Complex 3:[Zn₃?L???-OAc?₂?CH₃OH??H₂O?]·2CH₃OH Empirical formula,C₃₇H₄₂Zn₃N₆O₂₀,Formula weight,1086.87,Tetragonal,I4₁,Unit call dimensions:a=1.931492?17?nm,b=1.931492?17?nm,c=1.268982?15?nm,?=90°,Z=4,V=4.73414?10?nm³,R₁=0.0381,wR₂=0.1103;Complex 4:[Zn₃?L???-OAc?₂?H₂O?₂]Empirical formula,C₃₄H₃₂Zn₃N₆O₁₈,Formula weight,1008.76,Tetragonal,I4₁,Unit call dimensions:a=1.94446?8?nm,b=1.94446?8?nm,c=1.27986?6?nm,?=90°,Z=4,V=4.8391?5?nm³,R₁=0.0402,wR₂=0.1111;A new tetraoxime naphthalenediol-based bis?salamo?-type ligand H₄L² can be used as relay-sensor for selective detection of Zn²⁺and CN^-ions in aqueous organic solvents.By using different metal ions to conduct anti-interference experiments,it is found that H₄L² can be used as a relay sensor for the selective detection of Zn²⁺ions in aqueous organic solvents and show obvious fluorescence enhancement.The L-Zn²⁺complex obtained from the interaction with Zn²⁺ions can be used for selective detection of CN^-ions.Their recognition mechanisms were analyzed by Job plots,fluorescence titration,UV-vis titration and DFT theoretical calculation.The crystal structure of L-Zn²⁺complex was determined by X-ray crystallography,and characterized by Hirshfeld surface analysis,elemental analysis,IR and UV-vis spectra.In addition,the L-Zn²⁺probe with wide pH range adaptability and excellent stability also show high selectivity to CN^-ions.