Syntheses, Crystal Structure And Properties Of Ploynuclear Complexes And Coordination Ploymers With Aromatic Carboxylic Acids

In the field of crystal engineering, ploynuclear complexes andcoordination ploymers with aromatic carboxylic acids currently attractconsiderable interest. The diversity in the coordination modes of aromaticcarboxylic acids, so the structures of coordination polymers based onaromatic carboxylic acids are more complicated and novel. Beingattracted much people’s attention and interests, the metal complexes ofthe carboxylic acid have the potential diversity of structure and magneticproperties, adsorption, catalytic and luminescence and so on.In this thesis,15novel metal ploynuclear complexes andcoordination ploymers based on two different aromatic carboxylic acids(3-nitrophthalic acid and5-chlorosalicylic acid) and auxiliary ligand(2,2′-bpy,4,4′-bpy, phen and TBZ) have been synthesized with metal ionsCd2+, Zn2+, Co2+, Mn2+, Ni2+, Pb2+, namely,[Cd(3-NPA)(2,2′-bpy)(H2O)·H2O]2(1),[Cd2(3-NPA)(phen)4(H2O)2]2(2),[Cd2(3-NPA)2(TBZ)2(H2O)2]·2H2O (3),[Zn2(3-NPA)2(TBZ)2](4),[Co2(3-NPA)2(2,2′-bpy)2(H2O)2]·2H2O (5),[Mn2(3-NPA)2(4,4′-bpy)3(H2O)6]·(4,4′-bpy)(6),[Zn2(3-NPA)2(4,4′-bpy)2H2O]n(7),[Co(3-NPA)(4,4′-bpy)H2O]n(8),[Ni(3-NPA)(4,4′-bpy)H2O]n(9),[Zn(3-NPA)(phen)(H2O)]n(10),[Zn2O(3-NPA)(TBZ)(H2O)]n(11),[Co(3-NPA)(TBZ)(H2O)]n(12),[Pb2O(3-NPA)]n(13),[Co(HL5)(4,4’-bpy)1.5(H2O)2]n·n(HL5)(14) and[Zn(HL5)2(4,4’-bpy)]n(15).In ploynuclear complexes (1)(6), the3-nitrophthalic acid adoptsμ2-η1:η1:η1:η0, μ2-η2:η0:η1:η0, μ2-η1:η0:η1:η0and μ1-η1:η0:η0:η0coordination modes to form four0D binuclear complexes (1),(3),(4),(5), (6) and a tetranuclear complex (2). Each4,4′-bpy acts as μ2-bridgelinking two metal centers to form three two-dimensional networkcoordination ploymers (7)–(9).3-Nitrophthalic acid adopts μ2-η1:η1:η1:η0and μ3-η1:η1:η1:η0coordination modes to form three one-dimensionalchain coordination ploymers (10)–(12). The four Pb(II) ions form atetranuclear unit [Pb4(μ4-O)2]4+through bonding from one bridging μ4-O,each irregular polyhedron Pb4O2cluster is linked to two neighboring3-NPA2-ligands to form a2D network coordination polymer (13).Polymer (14) exhibits one-dimensional infinite ladderlike chain. Inpolymer (15),4,4’-bpy acts as a bidentate ligand to bind Zn(II) ions toform a infinite zigzag chain structure.The weak O H···O hydrogen bonds and C H···O weaknonclassical hydrogen bonds as well as π-π stacking also play importantroles in affecting the final structure. All of them were characterized by IRspectra, elemental analysis, powder X-ray diffraction, fluorescenceproperties and thermal decomposition process.