Syntheses,Structures And Properties Of V-shaped Bidentated Carboxylate Acids Coordination Polymers

This dissertation consists of three parts. Firstly, we design and synthesize a V-shaped bidentated carboxylate acids ligand 4,4’-dicarboxydiphenylamine (H2L), and synthesized four coordination polymers with novel frameworks and properties by solvothermal or hydrothermal reactions. Secondly, we adopt 4,4’-dicarboxydiphenylamine with imidazole ligands synthesized eight coordination compounds with novel structures and properties. Thirdly, we adopt 4,4’-dicarboxydiphenylamine with pyridine ligands synthesized eight coordination compounds with novel structures and properties.1. Syntheses, Structures, and Properties of Coordination Polymers Based on V-shaped 4,4t-dicarboxydiphenylamineSolvothermal or hydrothermal reactions of 4,4’-dicarboxydiphenylamine (H2L) with transition salts in solvents yielded four new complexes, namely, [Cu(L)(DMF)·5/2H2O]n (1), [Cu2(L)2(H2O)2·3/2H2O]n (2), [Cu(L)(H20)H2O]n (3), [Cd2(L)2(DMF)2(H2O)4·DMF·4H2O]n(4).If V-shaped ligands assembly with metal clusters, such as the four-connected paddle-wheel SBUs, we wonder what would be happened? We supposed there are two possibilities for constructing infinity frameworks:one way is the up-up-down-down (type I), and the other way is up-down-up-down (type II). Since H2L is a flexible V-shaped ligand, more possibilities would be happen to the final frameworks. So we try to find out what possibilities we would get, if we adjust the synthesis conditions. What we also trying to do is to simplify the crystal synthesis as far as possible, such as avoid adding co-ligand during the synthesis procedure.As we expected, by the systematic variation of solvent, three unprecedented novel MOFs are obtained:compound 1 with three fold interpenetrated lvt topology; compound 2 with three fold interpenetrated dia topology; and compound 3 with five fold interpenetrated lvt topology. The accessible total volumes for compound 1 and compound 2 are -27% and -47%, respectively, and for compound 3 there is no accessible volume during the high degree interpenetration. This presents an amazing example of control over the topology, interpenetration and porosity of MOFs via solvent by the assembly of flexible V-shaped ligand and paddle-wheel SBU. Coupound 1 crystallize in orthorhombic space group Fddd. the SBUs and V-shaped ligands assembly with configuration in the way of up-up-down-down. The metallocyclic ring is a rhombic structural unit [Cu2(L)2]s with a very large cavity (ca. 50.0-22.8 A). Coupound 2 crystallize in orthorhombic space group I4122. the SBUs and V-shaped ligands assembly with configuration in the way of up-down-up-down. The metallocyclic ring [Cu2(L)2]6 is a chair-form structure with a large cavity (ca. 37.6-16.6 A). Coupound 3 crystallize in orthorhombic space group I41/a. the SBUs and V-shaped ligands assembly with configuration in the way of u up-up-down-down. The twist square metallocyclic ring of 3 contains four Cu2(CO2)4 SBUs and four L2-ligands (diagonal, ca.20.0× 20.0 A).Compound 4 crystallizes in a chiral space group P21. The crystal unit contains two [Cd(L)(DMF)(H2O)2] units, four free water molecules and one free DMF molecule, which are chemically identical but not related by crystallographic symmetry. [Cd(L)(DMF)(H2O)2] units connect to each other leading to a neutral 1-D polymeric chain structure. Due to the unrelated crystallographic symmetry, there exist two different 1-D polymeric chains and exhibit mirror-related conformations. The chains are held together forming into a three dimensional supramolecule via strong hydrogen bondings. These free solvent molecules (water and DMF) accompany with the oxygen from coordinated water and carboxyl to form single right-handed helical chains via O-H···O hydrogen bondings. Hydrogen bonds play a vital role in chirality transfer within the crystal. The most remarkable structural feature is that the stretch direction of the hydrated helixes are perpendicular to the stretch direction of [Cd(L)(DMF)(H2O)2]n chains. To the best of our knowledge, such solvent-assisted chiral helical chain which perpendicular to the host coordinated chain has not been reported in synthetic homochiral crystal hosts.2. Syntheses, Structures, and Properties of Coordination Polymers Based on V-shaped 4,4’-dicarboxydiphenylamine and imidazole ligandsSolvothermal or hydrothermal reactions of 4,4’-dicarboxydiphenylamine (H2L) with 4,4’-bis(imidazol-1-yl)phenyl (BIP),4,4’-bis(imidazol-1-yl)diphenyl (BIBP),2,6-bis(imidazol-1-yl)furan (FBIP) and 4,4’,4"-tri(imidazol-1-yl)phenyl (TIBP) in the presence of transition salts in solvents yielded eight new complexes, namely, [Co2(L)2(BIP)2·3H2O]n (5), [Co(L)(BIP)-2CH3CN]n (6), [Co(L)(BIBP)-H2O]n (7), [Cd(L)(BIBP)]n (8)å'Œ[Zn(L)(BIBP)]n (9), Cd(L)(BIP)0.5 H2O·DMF-2H20]n (10), [Zn(L)(TIBP)]n (11), Cd2(L)2(FBIP)2-2H2O]n (12).Compound 5 contains Co2(COO)2 cluster, the two pairs of BIP ligands almost in parallel, which linked two binuclear Co clusters with L2- to form a 3D framework. And topology analysis reveals cds topology. It is interesting to note that unlike other cds type MOFs, Compound 5 is a rare example of a cds type framework that is not interpenetrated. Most cds type frameworks are interpenetrated due to the self-duality of the cds net. Compound 5 and Compound 6 are two crystals resulting in solvents change. When using CH3CN/H2O instead of DMF/H2O as solvent, Compound 6 possessing unusual 2Dâ†'2D polycatenation of (4,4) nets is obtained. Compound 7 solved in the space group P21/c. The H2L displays an unusual mode of coordination with two carboxyl groups deprotonated, but only one O atom from one carboxyl group coordinates to Co atom, the other one uncoordinated carboxylate like a freely dangling arm fill in the grids, resulting a 2D sheet structure. Further form 3D supermaolecules via hydrogen bonds. Compounds 8 and 9 are isomorphous, crystallized in triclinic space group P1. Metal cation, L2- and BIBP ligands connected to a 2D sheet structure. Compound 10 crystallized in triclinic space group P1. Cd cation, L2- and BIP ligands connected to a 2D sheet structure. Compound 11 crystallized in triclinic space group C2/c. One of the N atom of TIBP did not coordinate to Zn. The structure is a 2D sheet, and form in 3D surperamolecule by weak interactions. Compound 12 crystallized in triclinic space group P1. Cd cation, L2- and FBIP ligands connected to a 2D sheet structure. And form 3D surperamolecules by Ï€-Ï€ interactions.3. Syntheses, Structures, and Properties of Coordination Polymers Based on V-shaped 4,4’-dicarboxydiphenylamine and pyridine ligandsSolvothermal or hydrothermal reactions of 4,4’-dicarboxydiphenylamine (H2L) with PHEN, BPY, DPEA, DPP, BYBP and DPNDI in the presence of transition salts in solvents yielded eight new complexes, namely, [Zn(L)(PHEN)H2O·H2O]n (13), Cd(L)(BPY)·H2O]n (14), [Co(L)(BPY)1.5]n (15), Cd(L)(DPEA)(H2O)·H2O]n (16), [Zn2(L)2(DPP)]n (17), [Zn(L)(BYBP)0.5DMF]n (18), [Co(L)(DPNDI)0.5]n (19), [Co(L)(BYBP)0.5]n (20). Compound 13 crystallized in monoclinic space group C2/c. The L2- ligands link the Zn (II) cations and PHEN ligands to an infinitely chains. The dangling PHEN groups are perpendicular to the propagation direction of the chain and bristle out in opposite directions. This arrangement paves the way for interdigitation via Ï€-Ï€ interactions. Pair A chains exist large hole rings constructing by four PHEN ligands (Ï€-Ï€ interactions), L2" ligands and four Znl centers. And pair B chains go through these rings in pair A resulting a 3D superalmolecule structure with large channels. Compound 14 crystallized in monoclinic space group C2/c.Cd clusters [Cd2(COO)4N2] are connected to four L2- ligands and four BPY ligands to form double layer grids. Compound 15 crystallized in monoclinic space group C2/c.Co clusters [Co2(COO)4N2] are connected to four L2- ligands to form sheets with lager cavities. The sheets are connected by BPY ligands to form 3D framework. The channels are filled with free BPY ligand. The topology analysis shows a six connected{44.611} net. Compound 16 crystallized in monoclinic space group C2/c.DPEA ligands have two configurations:trans and cis. Cd connected to L2- ligands and DPEA ligands to form 2-fold 3D framework. The topology analysis shows a cds net. Compound 17 crystallized in monoclinic space group C2/c.Zn connected to L2- ligands and DPP ligands to form 4-fold 3D framework. The topology analysis shows a six connected pcu net. Compound 18 crystallized in monoclinic space group C2/c.Zn connected to L2" ligands and BYBP ligands to form 1D zigzag ladder chains. The chains are further catenated together to form 2D sheets. Compounds 19 and 20 are isomorphous. Compound 19 crystallized in charity space group P43212. Co connected to L2-ligands and DPNDI ligands to form 3D framework. The topology analysis shows a jsm net. This is the first example of 3-fold jsm net.