Synthesis, Crystal Structures And Luminescent Properties Of The Coordination Compounds Based On Chiral Ligands And Different N-Donor Auxiliary Ligands

Recently, chiral coordination polymers, have received extensive attention, not only because of their diverse topologies and intriguing structure, but also for their potential applications in enantioselective synthesis, asymmetric catalysis, nonlinear optical materials, luminescence and magnetic materials. The most direct route is using the chiral ligands to prepare the bulk homochiral MOFs materials. Therefore, we selected N-benzoyl-L-glutamic acid and(S)-(+)-mandelic acid as ligands and a series of N-donor ligands as assistant ligands to synthesize chiral coordination compounds. In this paper, the main results are as follows:First, eight coordination compounds constructed by N-benzoyl-L-glutamic acid: [Zn(bzglu O)(2,2’-bipy)(H2O)]n(1); [Cd(bzglu O)(2,2’-bipy)(H2O)]n(2); [Cd8(bzglu O)8(2,2’-bipy)8·18H2O](3); [Cd(bzglu O)(2,4’-bipy)2(H2O)·3H2O]n(4); [Cd(bzglu O)(phen)·H2O]n(5); [Cd(bzglu O)(4,4’-bipy)(H2O)]n(6); [Cd(bzglu O)(bpp)(H2O)·2H2O]n(7); [Cd(bzglu O)(bpp)2·5.2H2O]n(8).(H2bzglu O = N-benzoyl-L-glutamic acid, 2,2’-bipy = 2,2’-pyridine, 2,4’-bipy = 2,4’-bipyridine, phen = 1,10-phenanthroline, 4,4’-bipy = 4,4’-bipyridine, bpp = 1,3-di(4-pyridyl)propane), which are characterized by X-ray crystallography, elemental analysis, IR spectra, thermal stability, powder X-ray diffraction and circular dichroism. Furthermore, The solid state luminescent property of the complexes 1-2 and 4-7 were studied.Compounds 1 and 2 crystallize in chiral space groups P212121 and exhibit one-dimensional(1D) straight chain structures, The chains are further linked via hydrogen bonds and π-π interactions to generate 2D supramolecular architecture. Compound 3 crystallizes in chiral space groups P21 and features a 0-D structure,which analysis revealed that four Cd2+ and four bzglu O2- are arranged alternately to form a novel bilayer metallomacrocycle in the porous material. Neighboring units are further linked by hydrogen bonds and π-π interactions to form a 3D supramolecular architecture. Compound 4 crystallizes in chiral space groups P212121 and features a 1D structure. The 1D chains are parallelly arranged, which are further extended into a 3D supramolecular network by many strong hydrogen bonds. Further research finds that there exist right-handed helical chains R-[H2O- H2O]n in the 3D supramolecular network linking by hydrogen-bonding interaction. Compound 5 crystallizes in achiral space groups Pī and features 1D double chain structures, which are further extended into a 2D supramolecular architecture through π-π interactions. Compound 6 crystallizes in achiral space groups Pī and features 2D layer structures, which are extended to supramolecular 3D supramolecular architecture by hydrogen bonding. Compounds 7 and 8 crystallize in chiral space groups P212121 and exhibit 2D structures. Compound 8 are further extended into a 3D supramolecular architecture through strong hydrogen bonds interactions. Circular dichroism spectra of compounds 1, 2, 4 and 7 confirm that the entire crystal products of 1,2, 4 and 7 are homochiral. Furthermore,The luminescent properties of the complexes 1-2 and 4-7 have been examined in solid states at room temperature, The different ancillary ligands, not only affect the structures of the complexes, but also affect the fluorescence properties of complexes.Second, five homochiral coordination compounds constructed by S-(+)-mandlic acid:[Co(Hmand)2(2,2’-bipy)?H2O](9); [Zn(Hmand)2(2,4’-bipy)(H2O)?2H2O](10); [Zn(Hmand)(bpe)(H2O)?(Cl O4)?H2O]n(11); [Zn(Hmand)(4,4’-bipy)(H2O)?(Cl O4)]n(12); [Pb(Hmand)(4,4’-bipy)(NO3)(H2O)?(H2O)]n(13)(H2mand =(S)-(+)-mandelic acid, bpe = 1,2-bis(4-pyridyl)methane) have been synthesized and characterized by X-ray crystallography, elemental analysis, IR, thermal analysis, powder X-ray diffraction and circular dichroism. Furthermore, The solid state luminescent property of the complexes 10-12 were studied.Compound 9 crystallizes in chiral space groups P6122 and features a 0D structures, which are extended to supramolecular 1D chain by hydrogen bonding. Compound 10 crystallizes in chiral space groups P21 and displays a discrete molecular units. Neighboring units are further linked by hydrogen bonds and π-π interactions to form a 3D supramolecular architecture. Compound 11 crystallizes in chiral space groups P21 and displays a 2D undulated network, which are further extended into a 3D supramolecular architecture through hydrogen bonds interactions. Compound 12 crystallizes in chiral space groups P21 and possesses a 2D sheet structure. Compound 13 crystallizes in chiral space groups P21 and displays a 2D structures, which are further extended into a 3D supramolecular architecture through hydrogen bonds interactions. Compounds 9-13 crystallize in chiral space groups, and their circular dichroism spectra exhibit obvious positive Cotton effects. Furthermore, The different of ancillary ligands, not only affect the structures of the complexes, but also affect the fluorescence properties of complexes.