Study On Syntheses,Crystal Structures,Hirshfeld Surfaces Analyses And Fluorescence Properties Of Salamo-type Ligands And Their Cobalt(?),Nickel(?),Copper(?)and Zinc(?)Complexes

As is well known to the public,in recent years,both transition metal complexes and rare earth metal complexes have been extensively studied,and they have also received a lot of scientific research in modern coordination chemistry and organometallic chemistry The favor of the people.Nowadays,with the rapid development of the discipline of modern coordination chemistry,the synthetic routes of metal complexes and related research on their properties have also become one of the hot research topics in more and more research groups.First,Salamo-type ligands have many advantages,for example:they have excellent stability,are not easy to hydrolyze during the reaction,and are particularly prone to coordination reaction with transition metal salts to form relatively stable transition metal complexes and many more.Secondly,in terms of complexes,the development of Salamo transition metal complexes has gradually evolved from simple structures such as mononuclear and binuclear to multinuclear metal complexes.So far,experts and scholars have prepared not only structures It is a relatively novel metal complex with a wide range of uses.There are many hydrogen bonds and CH�? interactions in this kind of metal complexes,and the two-dimensional or three-dimensional supramolecular structure can be formed through the self-assembly of hydrogen bonding.It also has a wide range of applications in the professional field,especially in the fields of nonlinear optics,catalysis,biological activity,and magnetic materials,which have shown their unique properties and potential application prospects.It can be said that the research on the design and synthesis of Salamo ligands and their metal complexes is of great significance and value.In this thesis,two Salamo-like ligands and their corresponding metal complexes were designed and synthesized,and their structures were characterized by elemental analyses,infrared spectra and ultraviolet absorption spectra et al.1.Preparations of semi-Salamo-like ligand HL and single Salamo-like ligand H3LFirst,a diamine 1,2-diamineoxyethane was synthesized;5-Nitrosalicylic aldehyde and 3-m ethoxy salicylic aldehyde were selected as the reaction raw materials.The optimal reaction temperature,type and proportion of solvent were selected using the synthesized diamine to react with 5-nitrosalicylic aldehyde,hemi-salamo-like ligand HL was obtained;using 1,2-diamineoxy ethane with 3-methoxysalicylic aldehyde,the intermediate(m ethoxy monocondensation compound)was obtained;the methoxy monocondensation compound was further reacted with other salicylaldehyde derivatives(3-hydroxysalicylaldehyde)to obtain N2O4 mono-salamo-like bisoxime ligand H3L.And through the study of fluorescence emission spectrum,the optimal excitation wavelengths of these two ligands and their maximum emission wavelengths were determined.2.Preparations of transition metal complexes based on the semi-Salamo-like ligand HLTwo metal complexes 1 and 2 were prepared by reacting the ligand HL(2-[O-(1-ethyloxyamide)]oxime-4-nitrophenol)with transition metal salts(copper acetylacetonate and copper acetate monohydrate)[{(L1)Cu}2(CH3OH)]�CH3OH(1)and[Cu(L2)2](2),and the crystal structures of these two complexes were determined by X-ray single crystal diffraction analysis.It was characterized by elemental analyses,infrared spectroscopy,ultraviolet-visible spectroscopy and Hirshfeld surfaces analyses.Single crystal X-ray crystallography showed the existence of intra-and intermolecular hydrogen bonding interactions in complexes 1 and 2 Through Hirshfeld surfaces analyses and two-dimensional fingerprints,O�H/H�O,C�H/H�C,and H�H can be clearly observed in complexes 1 and 2.The proportion of equal short-range action indicates that complexes 1 and 2 can exist stably.Finally,it can be shown by fluorescence spectroscopy that the ligand HL has a relatively strong fluorescence intensity,but the complexes 1 and 2 show weaker emission peaks than the ligand HL.3.Preparations of transition metal complexes based on the semi-Salamo-like ligand HLThrough the teaction of a single Salamo-like bisoxime ligand H3L(6-Hydroxy-6'-methoxy-2,2'-[ethylenediyldioxybis(nitrilomethylidyne)]diphenol)with a transition metal salt(cobalt acetate tetrahydrate,nickel acetate tetrahydrate and zinc acetate tetrahydrate)respectively,four homotetranuclear transition metal complexes 3-6,[{Co(L)(?-OAc)Co(CH3OH)2}2](3),[{Ni(L)(DMF)(?-OAc)Ni}2](4),[{Ni(L)(?-OAc)Ni(CH3OH)}2]�4CH3OH(5)and[{(Zn(L)(?-OAc)Zn(CH3CH2OH)}2](6)were prepared,respectively.The X-ray single crystal diffractometer was also used to determine their crystal structures,and the coordination environment of the transition metal atoms in the transition metal complexes 3-6 and the crystal structure of the complexes were clearly seen through X-ray crystallography.After research,it was found that the crystal structures of transition metal complexes 3-6 are similar.They all have abundant intramolecular and intermolecular hydrogen bonding interactions.In addition,we also used a number of commonly used methods to carry out a series of characterizations of the complexes 3-6,and carried out a systematic in-depth study on the synthesis methods,supramolecular effects and biological antibacterial activities of the transition metal complexes.Discussion research.And according to Hirshfeld surface analysis and two-dimensional fingerprints of complexes 3-6,O�H/H�O,C�H/H�C,and H�H,etc.can be observed the proportion of various short-range effects.