| The main research contents in this thesis are as follows:The two macrocyclic ligands1,4,7,10,13,16,21,24-octaazabicyclo [8.8.8]hexacosane (L0) and1,4,23,26,29,48-hexaaza-6,9:16,19:31,34:41,44-tetrabenzo-12,15,37,40-tetraoxa-cyclodotetracontane (L1) have been synthesized according to literature methods and explored as ligands with different metal salts and acids for preparing a variety of metal complexes and supramolecular compounds.Reactions between L0and several Cd(Ⅱ) salts (nitrate, benzoate, chloride, trifluoromethane sulfonate), Zn(Ⅱ) salt (chloride) and Co(Ⅱ) salts (nitrate, chloride) led to the formation of the complexes [CdL0]·(NO3)2(1),[CdL0]·Cd2(OCOPh)6·2H2O (2),[CdL0]·[CdCl4](3),[CdL0]·[Cd(H2O)6]·(CF3S-O3)4(4),[ZnL0(H2O)]·[Zn2Cl6(μ2-OHCO)]·H2O (5),[Zn,1.5L0]·[ZnCl4]·Cl·2H2O (6),[CoL2]·(NO3)3·H2O (7),[CoL0·H2O]·[CoCl4]·Cl·2H2O (8), which were characterized by single crystal X-ray diffraction. In (1) and (2), the center Cd(Ⅱ) ion is hexacoordinated, with a N6coordination environment and bipyramidal octahedral coordination geometries. Meanwhile, the other two cadmium ions in complex (2) are coordinated with six and eight oxygen atoms from six benzoate ligands, forming two distorted bipyramidal octahedral and pentagonal bipyramid coordination geometries, respectively; In (3) and (4), the center Cd(Ⅱ) ion is heptacoordinated, with a N7coordination environment and distorted bipyramidal octahedral coordination geometry. Another cadmium ion in complexes (3) and (4) are coordinated with four chloridion or six waters, forming tetrahedral and bipyramidal octahedral coordination geometry, respectively; In (5), the center Zn(II) ion is pentacoordinated, with a N4O coordination environment and a trigonal bipyramidal coordination geometry. Two zinc ions in complex (5) are coordinate with one oxygen from formate and three chloride auxiliary ligands, forming two tetrahedral coordination geometry; In (6), two center Zn(Ⅱ) ions both are tetracoordinated, with N3coordination environment and distorted tetrahedral coordination geometry. The two zinc are connected by metallic bonding, The Zn...Zn separation is2.324(8) A. Another zinc ion in complex (6) is coordinated with four chloride ligands, forming a tetrahedral coordination geometry; In (7), the center Co(Ⅲ) ion is hexacoordinated, with a N6coordination environment and distorted bipyramidal octahedral coordination geometries; In (8), one center Co(Ⅲ) ion is pentacoordinated, with a N4O coordination environment and trigonal bipyramidal hexahedral coordinate-on geometry. Another cobalt ion in complex (8) is coordinated with four chloride ligands, forming a tetrahedral coordination geometry. It’s interesting that Co(Ⅱ) in this complex was oxidized to Co(Ⅲ) by oxygen in the air after cobalt(Ⅱ) and the cryptand ligand form complex. Reactions between L1and several acids (p-toluenesulfonic acid, o-hydroxybenzoic acid, m-hydroxybenzoic acid) led to the formation of the three supramolecular compounds [H6L1]·(p-OCOPhOH-)6·2H2O(9),[H6L1(p-O-SO2PhCH3)2]·(p-OSO2PhCH3)4·7.5H2O(10),[H6L1(m-OCOPhOH)2(H2O)3]·(m-OCOPhOH)4·5H2O (11), which were characterized by1H NMR,13C NMR, single crystal X-ray diffraction and fluorescence spectroscopies. In (9), the six p-HOPhCOO-anions and two water molecules are located outside the cavity of the hexaprotonated crown ether [H6L1]6+; In (10), the four p-H3CPhSO3-anions and seven and half water molecules are located outside the cavity of [HML1]6+, and its cavity is occupied by two p-H3CPhSO3-anions; In (11), the four m-HOPhCOO-anions and five water molecules are located outside the cavity of [H6L1]6+, and its cavity is occupied by two m-HOPhCOO-anions and five water molecules. The crystal structures of supramolecular compounds (9),(10) and (11) showed that p-CH3PhSO3-and m-HOPhCOO-can facilely enter into the cavity of the [HeL1]6+, while p-HOPhCOO-can not be encapsulated inside the cavity of [H6L1]6+. This is because the packing mode of supramolecular compound (10) and (11) are different from (9), leading to the change of the ring diameter and shape of the host crown ether and the results of some selectivity for the different anions. The results also show that these three supramolecular compounds have some fluorescence properties and can be used as potential optical materials. |
PDF Full Text Request