Synthesis And Structure Of Coordination Polymers Constructed From Coordination Compound Containing Phenanthroline As Precursor

Coordination polymers are 0D, 1D, 2D and infinite 3D networks constructed through coordination bonds between metal ions and appropriate organic ligands. Coordination polymers possess both the rigid structure of inorganic compounds and the functionality of organic compounds, which bring them potential applications in the fileds of magnetics, non-linear optics, catalysis, chiral recognition and separation etc. So, the design and synthesis of functional coordination polymers have been attracted much attentions.Here, we design novel coordination polymers through the design of the coordination compounds as precursor. Coordination compound, Cu(phen)₂Cl₂, was design and synthesized from phenanthroline (phen) as organic ligand because its good repeatability of synthesis, high productivity and purity. And the precursor containing phen ligand can form [Cu(phen)₂]²⁺ cation, which can further coordinate with anionic ligands to construct new coordination polymers. In the synthesis, the precursor can retain its structure partly or entirely, which favors the formation of coordination polymers with novel topology.1. The synthesis of precursors:The phenanthroline as synthesized Cu (phen)₂Cl₂ (1) and[Cu(phen)₂Cl·(OH)]·H₂O (2) two kinds of coordination compounds. Compounds (1) is coordinated by two chelating o-phenanthroline and the two end groups with the formation of chloride ion zero-dimensional structure. Compounds (2) is coordinated by two chelating o-phenanthroline ligand and one terminal chloride ions in [Cu(phen)₂Cl]⁺ cation, free of hydroxyl ions in the structure plays a balancing The role of charge.2. The synthesis of coordination polymers from the precursor of Cu (phen)2Cl2:(1) reaction of precursor compounds Cu(phen)₂Cl₂ (1) in the synthetic system can provide [Cu(phen)²]²⁺ or [Cu(phen)²Cl]⁺ cation, choose organic acid ligand (benzene dianhydride and terephthalic acid) as the anionic ligands is the synthesis of coordination polymers were obtained [Cu(phen)₂Cl]⁺·[C₁₀H₅O₈]- (3) , [Cu(phen)₂Cl]⁺·0.5[C₁₀H₄O₈]^2- (4) , Cu(phen)Cl (BDC)_0.5 (5) and Cu(phen)(BDC) (6) four kinds of coordination polymers. Compounds (3) is [Cu(phen)₂Cl]⁺ cation and not involved in the coordination of all benzene dianhydride ligand formed by hydrolysis of pyromellitic acid carboxyl proton off a H3betc- anion formed after the formation of the zero dimensional structure, which H3betc-anion balance in the structure play only the role of the charge. Compounds (4) is [Cu(phen)₂Cl]⁺ cations and 0.5 are not involved in the coordination of the ligand benzene dianhydride pyromellitic formed by hydrolysis of a carboxylic acid proton off H2betc^2-anion formed after the formation of zero-dimensional structure, H₂betc^2- anion in the structure of the same playonly the role of charge balance. Compounds (5) is terephthalic acid ligand bridging the two[Cu(phen)₂Cl]⁺ dual-core copper between the structural unit. Adjacent structural units usedual-core copper phenanthroline ligandπ→πstacking between the role of thezero-dimensional structures to expand into one-dimensional chain structure. Compounds (6)is bridged by the acid in the [Cu(phen)₂]²⁺ formed between the one-dimensional zigzag chainstructure, the adjacent one-dimensional chain between the two can be between phenπ→πstacking interactions forming three-dimensional supramolecular structure.(2) Reaction precursor of Cu(phen)₂Cl₂ (1) in the synthetic system provides[Cu(phen)₂]²⁺ cations to [Fe(CN)]₆^3- as the anionic ligands is the synthesis of coordinationpolymers, obtained coordination polymer {[Cu(phen)₂]₃[Fe(CN)₆]}₂·2[Fe(CN)₆] (7).Compounds (7) the existence of two identical structure {[Cu(phen)₂]₃[Fe(CN)₆]}³⁺ structuralunit, each unit is a structure of an iron cyanide anions by the use of its structure respectivelyin the three cyano three [Cu(phen)₂]²⁺ in the formation of copper coordinationzero-dimensional structure. Two free iron cyanide anion played a role in balancing the charge.