Self-Assembly Of Supramolecular Coordination Polymers Controlled By Using 2-Phenyl-1H-1, 3, 7, 8-Tetraazacyclopenta[L]-Phenanthrene And Aromatic Acid Ligands

With the rapid development of the organic chemistry and inorganic chemistry, the coordination chemistry become the focus of the synthesis of new solid material. More and more new polymers are synthesized and depositted in CCDC in the form of crystal. At the same time, the supramolecular chemistry has a great progress in the recent years. So metal-containing supramolecular has rapidly emerged as a hot subject and more and more amusing coordination supramolecular polymers have been researched in literature. But there is still a lack of an effective method to control the structures.In this paper we have selected the 2-phenyl-1H-1,3,7,8-tetraazacyclopenta[1]-phenanthrene (PTCP) as the multi-nitrogen ligand which contains five condensation rings and four nitrogen atoms, two at the phenanthroline moiety and two nitrogens from the imidazole portion. The ligand can coordinate with most of the transition metal ions and rare metal ions. The imidazole rings in this ligand is both the H-donor and H-acceptor which are good candidates to cunstruct new coordination supramolecular structures. At the same time, the aromatic acid can coordinate with most of the metal atoms which can be selected as the bridge ligands.Nineteen novel coordination complexes [Eu2(BDC)3(H2O)]n (1); [Pb3(BTC)2(H2O)]n(2); [Pb3(BTC)2 (H2O)2]n·n(H2O)3.5 (3); [Ni2(PTCP)4(SO4)(H2O)3] [(SO4)(H2O)4.5] (4); [Fe(PTCP)3][(SO4)(H2O)7] (5); [Co2(PTCP)2(3,5-NSYS)2(H2O)2] (6); [Zn(PTCP)2(5-SSYS)(H2O)] (7); [Pb2(PTCP)2(BTC)2] (8); [Ln2(PTCP)2(m-BDC)3]n·0.5n(H2O) (Ln=Ce,Pr,Nd,Sm,Eu,Tb,Dy,Tm) (9-16); [Co(PTCP(LBSS)(H2O)2]n·n(H2O) (17); [Pb(PTCP)(PYDC)]n·0.5n(H2O) (18); [Cu(PTCP)(PTA)]n (19) have been hydrothermally synthesized and characterized by IR spectra, Elemental analyses, TGA, X-ray single-crystal diffraction and solid-state photoluminescent spectra. Complex 1-3 represent the new 2D or 3D inorganic-organic polymeric structure constructed by aromatic carboxylic acid and transition metal ions. Complex 4 and 5 are 3D coordination supramolecular polymers formed form OD structure. Both polymers are constructed by PTCP and inorganic metal salt. Complexes 6-19 are constructed by PTCP and aromatic carboxylic acid ligands. These polymers are the 2D or 3D supramolecular structure which are constructed form OD or 1D structure.In this paper, a new method is found to control the dimension by using the PTCP ligand:(1) When the single multi-aromatic acid is used as the organic ligand, the high dimensional (2D or 3D) polymers can be formed;(2) When the PTCP ligand and the analog are used as the single-ligand, low dimensional (OD) polymer can be synthesized, but the OD structure can be grown to high dimensional (2D or 3D) supramolecular structure;(3) When the PTCP and multi-aromatic acid ligands are mixed-used, OD or 1D multi-nuclear polymers can be self-assembled in to the 3D supramolecular structure. In the most case, the multi-aromatic acid ligands used as the bridge ligands and the PTCP ligand is the key point of constructing the hydrogen-bond net. The 1D or OD is rest with the steric effect and the tractility of the carborxylic acid ligands.(a) When single-carborxylic acid ligands (salicylic acid) are selected to mixed-used with ligands (such as PTCP) which have big steric effect and single coordinate site, OD polymers can be constructed and extended to 3D supramolecular structure via H-bonds.(b) When multi-carborxylic acid ligands (such as 1,3-benzenedicarboxylic acid, 1,3,5-benzenetricarboxylic acid, pyridine-2,5-dicarboxylic acid, and so on) with big steric effect are selected to mixed-use with ligands (such as PTCP) which have big steric effect and single coordinate site, 1D chian polymers can be constructed and extended into 3D supramolecular structure via H-bonds and stacking interactions.(c) When multi-carborxylic acid ligands (such as 1,4-benzenedicarboxylic acid) with small steric effect and good tractility are selected to mixed-use with ligands (such as PTCP) which have big steric effect and single coordinate site, 2D polymers can be constructed and extended into 3D supramolecular structure via H-bonds and stacking interactions.