The Design, Synthesis, Structure And Porperties Of Complexes Based On Asymmetrical Aroylhydrazone Ligand

Acylhydrazone Schiff base system is an important branch and important research areaof Schiff base. The controllable synthesis of functional acylhydrazone complex withpre-designed structures and properties is a frontier and also a challenging task. Herein，32complexes with the designed aroylhydrazone Schiff base ligands have been synthesized andstudied. These complexes are further characterized by FT-IR, elemental analysis, UV-vis,X-ray powder diffraction, thermogravimetric analyses, and single crystal X-ray diffractions.Zn and Cd complexes are also characterized by fluorescence analyzer. The mainexperimental results are as follows:1. Four novel complexes have been synthesized by assemble of the designedaroylhydrazone Schiff base ligand H3L1(4-Hydroxy-benzoic acid (2-hydroxy-benzylidene)-hydrazide) and the Cu/Ni/Zn salt with controlling the structural diversities throughsynthesis method and the secondary ligand.[Cu (H2L1)(Me2NCO)]2(1)[Cu (H2L1)(NO3)]·H2O (2)[Ni (H2L1)2]·3DMSO·H2O (3)[Zn2(H2L1)2(4,4′-bipy)(H2O)2](NO3)2(4)Complexes1and2are mononuclear and binuclear Cu complex, respectively. Incomplex1, DMF acts as anion to coordinate Cu ion. To the best of our knowledge, this isthe first example that DMF acts as anion coordinating with metal ions in aroylhydrazonecomplex. In2, the H-bonding constructed the helices which are all right-handed and theoverall structure can be viewed as homochiral supramolecular framework. Complex3ismononuclear Ni complex. By the employment of linear bridge ligand4,4′-bipy，binuclearZn complex4is obtained. The luminescent properties of4have been investigated, whereoccurs blue-shifted and4emits strong green luminescence.2. Thirteen novel complexes have been synthesized by assemble of Cu/Zn/Cd salt andthe designed aroylhydrazone Schiff base ligand H3L2((E)-4-hydroxy-N’-((2-hydroxynaphthalen-1-yl)methylene)benzohydrazide) while controlling the structuraldiversities through anions and the secondary ligands.[Cu (H2L2)(CH3OH)2] NO3(5)[Cu (H2L2)(NO3)(H2O)]·H2O (6) [Cu(H2L2)Cl]·2H2O (7)[Cu(H2L2)(CH3OH) Cl]·CH3OH (8)[Cu(HL2)(H2O)]·CH3OH (9)[Cu(H2L2)(SCN)(DMF)]·DMF (10){[Cu(H2L2)(4,4′-bipy)] ClO4·4DMF}n(11)[Zn (H2L2)2]·2DMF·H2O (12){[Zn(H2L2)(4,4′-bipy)]ClO4·DMF·CH3CN}n(13){[Zn(H2L2)(bpe)]NO3·DMF·CH3CN}n(14)[Zn2(H2L2)2(bpa)(H2O)2](ClO4)2·6DMF (15)[Cd(H2L2)2]·2DMSO (16){[Cd (4,4′-bipy)2](ClO4)2·2H3L2·4CH3OH}n(17)With different Cu salts (Cl-, NO3-, ClO4-, CH3COO-) and solvents, five different kindsof mononuclear Cu complexes5-9are obtained. By the employment of the distinctsecondary ligands SCN-and4,4′-bipy，mononuclear Cu complex10and1D coordinationcomplex11were constructed. However, the ligand is predominantly in the enolate form tocoordinate to Cu ion only in9.Complexes12and16are mononuclear Zn and Cd complex, respectively. The linearbridge ligands4,4′-bipy,1,2-di-(pyridin-4-yl)ethylene(bpe) and1,2-di-(pyridin-4-yl)ethane(bpa), are chosen to construct binuclear Zn complex15,1D coordination Zn complexes13and14,2D coordination Cd complex17. The luminescent properties of complexes12-15have been investigated. The stronger rigidity of the secondary ligand is with, the longerfluorescence wavelength was appeared. Complex14(bpe as a secondary ligand) emitsorange fluorescence while complex13(4,4’-bipy as a secondary ligand) exhibits yellowfluorescence. Complex12exhibits yellow-green fluorescence and complex15(bpa as asecondary ligand) exhibits green fluorescence.3. Ten novel complexes have been synthesized by assemble of Cu/Co/Zn/Cd/Dy saltand the designed aroylhydrazone Schiff base ligand H4L3((E)-N’-(2,3-dihydroxybenzylidene)-4-hydroxybenzohydrazide). Mononuclear, binuclear, trinuclear,tetranuclear, tridecanuclear and1D coordination complexes were obtained.[Zn4(H2L3)4]·3DMF·3H2O (18)[Zn4(H2L3)2(CH3COO)4]·2DMF·2CH3OH (19)[Cd2(H3L3)2(DMF)4](NO3)2·2CH3CN (20) {[Cd2(H3L3)(H2L3)(bpa)(EtOH)(MeOH)]NO3·2DMF·EtOH·bpa}n(21)[Cd13(H2L3)4(HL3)2(CH3COO)12]·6H2O (22)[Cu (H3L3)(H2O)]NO3·2H2O (23)[Cu4(H3L3)4](NO3)4·2CH3CN·4H2O (24)[Co (H3L3)2]·2DMF·H2O (25)[Dy2(H3L3)2(NO3)4]·4CH3CN·2CH3OH (26)[Dy3(H2L3)2(CH3COO)5(DMF)3]·DMF·CH3OH·1.5H2O (27)Complex18and19are both tetranuclear Zn complexes. Complex18displayed a Zn4O4boat-shaped core. The moieties are self-assembled through the H-bonding into a two-foldinterpenetrated3D diamondoid network. Complex19presents a discrete linear tetranuclearZn structure. The solvent effects on photophysical properties of18and19are examinedand both18and19exhibit a wide range of luminescence in the different organic solvents.Complex20is a binuclear Cd complex, and21is a1D chain structure constructedfrom the dinuclear complex20as the SBUs connected by secondary ligand bpa. Complex22is a novel trideca-Cd cluster and exhibits an isolated windmill-shaped nanoplate oftridecanuclear Cd cluster. These tridecanuclear-Cd nanoplates are assembled to form2Dhoneycomb layer by H-bonding. The1D channel with a diameter of1.7nm exits in the3Dstructure. The luminescent properties of20and22have been investigated, that red-shiftsare occurred, and the complexes exhibit blue and green luminescence respectively.Distinct by solvent, complex23is monuclear Cu complex and complex24istetranulear cluster with cube-core. The complex25is monuclear Co complex. Complexes26and27are binuclear and trinuclear Dy complex, respectively. Research onsupramolecular structure of complex27shows that water clusters exist in3D framework.4. The binuclear Zn complex28is synthesized by assemble of Zinc acetate and thedesigned aroylhydrazone Schiff base ligand H3L6(4-Hydroxy-benzoic acid(2-hydroxy-5-nitro-benzylidene)-hydrazide). The discrete linear tetranuclear Zn complex29is synthesized by assembly of Zinc acetate and the designed aroylhydrazone Schiff baseligand H4L4(4-Hydroxy-3-methoxy-benzoic acid (2,3-dihydroxy-benzylidene)-hydra-zide). The1D chain Zn complex30was synthesized byassemble of Zinc acetate and the designed aroylhydrazone Schiff base ligand H2L5((4-Nitro-phenoxy)-acetic acid (2-hydroxy-3-methoxy-benzylidene)-hydrazide). The2D laystructure of complex31is synthesized by assemble of Zn salt, the secondary ligand (bpa) and the designed aroylhydrazone Schiff base ligand H4L8(4-Hydroxy-benzoic acid (2,4-dihydroxy-benzylidene)-hydrazide). The binuclear Cd complex32is synthesized byassembly of Cd salt and the designed aroylhydrazone Schiff base ligand H3L7((4-Nitro-phenoxy)-acetic acid (2,3-dihydroxy-benzylidene)-hydrazide). The luminescentproperties of29and30have been investigated, where occurs red-shifted and the complexesexhibit yellow-green fluorescence.[Zn (H2L6)(CH3COO)]2·CH3OH (28)[Zn4(H2L4)2(CH3COO)4]·4DMF (29){[Zn4(L5)2(CH3COO)4]·DMSO}n(30){[Zn (H3L8)(bpa)]ClO4·4CH3OH}n(31)[Cd2(H2L7)2(DMF)4](ClO4)2·4DMF (32)...