Synthesis,Crystal Structure And Properties Of 3d-4f Metal Complexes Constructed From A Multi-naphthol-based Bis(Salamo)-type Ligand And Fluorescence Sensor

In this work,a series of 3d,3d-4f metal complexes based on the reactions of a multi-naphthol-based bis（Salamo）-type ligand（H₄L）with transition metal ions and earth metal ions have been synthesized under certain conditions,respectively.The structures of all complexes were fully characterized by single crystal X-ray crystallography,elemental analyses,FT-IR and UV-Vis spectroscopy.Moreover,the fluorescence properties of 3d-4f complexes were in-depth studied.In addition,the electrochemical properties,fluorescence behaviors and antimicrobial activities of multi-naphthol-based bis（Salamo）-type ligand H₄L and its transition metal ions complexes have also been investigated.The detailed crystal data were as follows:Complex 1:Empirical formula,C₂₆H₂₂Cu₂N₂O₆,Formula weight,585.53,Monoclinic,P2₁/n,Unit call dimensions:a=5.309（3）?,b=18.225（9）?,c=11.643（6）?,β=98.394（7）°,Z=2,V=1114.4（9）?³,R₁=0.0435,wR₂=0.0955;Complex 2:Empirical formula,C₅₂H₄₀CuN₆Ni₂O₁₂,Formula weight,1121.86,Triclinic,P-1,Unit call dimensions:a=12.4369（12）?,b=13.3684（17）?,c=15.841（2）?,?=88.650（10）°,β=67.631（11）°,γ=78.818（10）°,Z=2,V=2385.7（5）?³,R₁=0.0900,wR₂=0.1243;Complex 3:Empirical formula,C₅₂H₄₀CuN₆Ni₂O₁₂,Formula weight,1121.86,Triclinic,P-1,Unit call dimensions:a=12.4369（12）?,b=13.3684（17）?,c=15.841（2）?,?=88.650（10）°,β=67.631（11）°,γ=78.818（10）°,Z=2,V=2385.7（5）?³,R₁=0.0900,wR₂=0.1243;Complex 4:Empirical formula,C₅₂H₆₁Co₂DyN₉O₂₁,Formula weight,1428.45,Monoclinic,P2₁/n,Unit call dimensions:a=9.2838（4）?,b=24.9653（11）?,c=12.7982（6）?,β=97.059（4）°,Z=2,V=2943.8（2）?³,R₁=0.0417,wR₂=0.1027;Complex 5:Empirical formula,C₈₀H₇₆Zn₄SmN₁₁O₃₁,Formula weight,2099.34,Orthorhombic,P2₁2₁2₁,Unit call dimensions:a=13.4214（2）?,b=25.3604（5）?,c=26.7104（6）?,Z=4,V=9091.5（3）?³,R₁=0.0492,wR₂=0.1084;Complex 6:Empirical formula,C₇₈H₆₉Zn₄GdN₁₁O₃₀,Formula weight,2059.17,Orthorhombic,P2₁2₁2₁,Unit call dimensions:a=13.4859（5）?,b=25.4470（7）?,c=26.8544（10）?,Z=4,V=9215.8（6）?³,R₁=0.0561,wR₂=0.0966;Complex 7:Empirical formula,C₇₉H₇₄Zn₄GdN₁₁O₃₁,Formula weight,2092.22,Orthorhombic,P2₁2₁2₁,Unit call dimensions:a=13.4859?,b=25.4470（7）?,c=26.8544（10）?,Z=4,V=9215.8（6）?³,R₁=0.0557,wR₂=0.1041;Complex 8:Empirical formula,C₈₁H₇₅Zn₄TbN₁₀O₂₇,Formula weight,2040.91,Orthorhombic,P2₁2₁2₁,Unit call dimensions:a=14.2429（8）?,b=25.0028（9）?,c=14.4213（7）?,Z=4,V=4771.3（4）?³,R₁=0.0585,wR₂=0.1449.Meanwhile,multi-naphthol-based bis（Salamo）-type ligand H₄L was used as a fluorescence sensor,sensor H₄L was found to have excellent selectivity for B₄O₇^2-and Cd²⁺ions in Tris-HCl buffer（DMF/H₂O=9:1,v/v,pH=7）solutions.The study results indicate that there were nearly no changes in the fluorescence intensity of detection process in different time,temperature and pH.The test strips could conveniently,efficiently and simply detect B₄O₇^2-and Cd²⁺ions in solutions.The detection limit of sensor H₄L towards B₄O₇^2-was 8.61×10^-77 M.Furthermore,sensor H₄L showed excellent membrane permeability in living cells,and it was successfully used to monitor intracellular B₄O₇^2-.