With regard to crystal engineering, building block or modular assembly methodologies have shown great success in the design and construction of metal–organic coordination polymers. The critical factor for the construction of coordination polymers is the rational choice of the organic building blocks and the metal centre. The reaction of Zn(OAc)2·2H2O (OAc is acetate) with 3‐nitrobenzoic acid (HNBA) and 4,4′‐bipyridine (4,4′‐bipy) under hydrothermal conditions produced a two‐dimensional zinc(II) supramolecular architecture, catena‐poly[[bis(3‐nitrobenzoato‐κ2O,O′)zinc(II)]‐μ‐4,4′‐bipyridine‐κ2N:N′], [Zn(C7H4NO4)2(C10H8N2)]n or [Zn(NBA)2(4,4′‐bipy)]n, which was characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis and single‐crystal X‐ray diffraction analysis. The ZnII ions are connected by the 4,4′‐bipy ligands to form a one‐dimensional zigzag chain and the chains are decorated with anionic NBA ligands which interact further through aromatic π–π stacking interactions, expanding the structure into a threefold interpenetrated two‐dimensional supramolecular architecture. The solid‐state fluorescence analysis indicates a slight blue shift compared with pure 4,4′‐bipyridine and HNBA. 相似文献
Two new one‐dimensional CuII coordination polymers (CPs) containing the C2h‐symmetric terphenyl‐based dicarboxylate linker 1,1′:4′,1′′‐terphenyl‐3,3′‐dicarboxylate (3,3′‐TPDC), namely catena‐poly[[bis(dimethylamine‐κN)copper(II)]‐μ‐1,1′:4′,1′′‐terphenyl‐3,3′‐dicarboxylato‐κ4O,O′:O′′:O′′′] monohydrate], {[Cu(C20H12O4)(C2H7N)2]·H2O}n, (I), and catena‐poly[[aquabis(dimethylamine‐κN)copper(II)]‐μ‐1,1′:4′,1′′‐terphenyl‐3,3′‐dicarboxylato‐κ2O3:O3′] monohydrate], {[Cu(C20H12O4)(C2H7N)2(H2O)]·H2O}n, (II), were both obtained from two different methods of preparation: one reaction was performed in the presence of 1,4‐diazabicyclo[2.2.2]octane (DABCO) as a potential pillar ligand and the other was carried out in the absence of the DABCO pillar. Both reactions afforded crystals of different colours, i.e. violet plates for (I) and blue needles for (II), both of which were analysed by X‐ray crystallography. The 3,3′‐TPDC bridging ligands coordinate the CuII ions in asymmetric chelating modes in (I) and in monodenate binding modes in (II), forming one‐dimensional chains in each case. Both coordination polymers contain two coordinated dimethylamine ligands in mutually trans positions, and there is an additional aqua ligand in (II). The solvent water molecules are involved in hydrogen bonds between the one‐dimensional coordination polymer chains, forming a two‐dimensional network in (I) and a three‐dimensional network in (II). 相似文献
Williamson type ether reactions were utilized for a high yield reaction of 4′‐chloro‐2,2′:6′,2″‐terpyridine with α,ω‐dihydroxy‐functionalized poly(ethylene oxide) and poly(oxytetramethylene)s to obtain bis(terpyridine)‐terminated telechelics. The completeness of the functionalization was proven by NMR spectroscopy, GPC and MALDI‐TOF‐MS investigations. The addition of transition metal ions resulted in a polyaddition polymerization leading to the formation of extended metallo‐supramolecular polymers, as proven by UV/VIS spectroscopy titration experiments. 相似文献
The reaction of Cu(NO3)2·3H2O with 2,4′‐oxybis(benzoic acid) and 4,4′‐bipyridine under hydrothermal conditions produced a new mixed‐ligand two‐dimensional copper(II) coordination polymer, namely poly[[(μ‐4,4′‐bipyridine‐κ2N ,N ′)[μ‐2,4′‐oxybis(benzoato)‐κ4O 2,O 2′:O 4,O 4′]copper(II)] monohydrate], {[Cu(C14H8O5)(C10H8N2)]·H2O}n , which was characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis and single‐crystal X‐ray diffraction. The X‐ray diffraction crystal structure analysis reveals that the CuII ions are connected to form a two‐dimensional wave‐like network through 4,4′‐bipyridine and 2,4′‐oxybis(benzoate) ligands. The two‐dimensional layers are expanded into a three‐dimensional supramolecular structure through intermolecular O—H…O and C—H…O hydrogen bonds. Furthermore, magnetic susceptibility measurements indicate that the complex shows weak antiferromagnetic interactions between adjacent CuII ions. 相似文献
Orthogonal self‐assembly of multiple components represents an efficient strategy to afford hierarchical and multifunctional assemblies. Here, we demonstrate the orthogonal recognition behaviors between benzo‐21‐crown‐7/secondary ammonium salt and terpyridine/metal ions (Fe2+ or Zn2+) recognition motifs. Main‐chain supramolecular polymers are subsequently achieved via “one‐pot” mixing of the three monomers together (heteroditopic monomer 1 , homoditopic secondary ammonium salt monomer 2, and Fe(BF4)2•6H2O or Zn(OTf)2), which are confirmed by 1H NMR, UV–Vis, DOSY, and viscosity measurements. Moreover, different metal ions (Fe2+ or Zn2+) exert considerable effects on the size of the resulting supramolecular polymers. Integration of two different types of non‐covalent interactions renders dynamic and responsive properties for the resulting supramolecular polymers, as triggered by a variety of external stimuli such as temperature, potassium cation, as well as stronger chelating ligands. Therefore, the current work is a prerequisite for the future application of such orthogonal assemblies as intelligent supramolecular materials.
The new synthesized ligand (DADMBTZ = 2,2′‐diamino‐5,5′‐dimethyl‐4,4′‐bithiazole), which is mentioned in this text, is used for preparing the two new complexes [Zn(DADMBTZ)3](ClO4)2. 0.8MeOH.0.2H2O ( 1 ) and [Cd(DADMBTZ)3](ClO4)2 ( 2 ). The characterization was done by IR, 1H, 13C NMR spectroscopy, elemental analysis and single crystal X‐ray determination. In reaction with DADMBTZ, zinc(II) and cadmium(II) show different characterization. In 2 , to form a tris‐chelate complex with nearly C3 symmetry for coordination polyhedron, DADMBTZ acts as a bidentate ligand. In 1 , this difference maybe relevant to small radii of Zn2+ which make one of the DADMBTZ ligands act as a monodentate ligand to form the five coordinated Zn2+ complex. In both 1 and 2 complexes the anions are symmetrically different. 1 and 2 complexes form 2‐D and 3‐D networks via N‐H···O and N‐H···N hydrogen bonds, respectively. 相似文献
Two metal‐organic coordination polymers with one‐dimensional infinite chain motif, [Cd(bqdc)(phen)2]n ( 1 ) and [Co(bqdc)(phen)(H2O)2]n ( 2 ) (H2bqdc = 2,2′‐biquinoline‐4,4′‐dicarboxylic acid, phen = 1,10‐phenanthroline), have been synthesized under similar solv/hydrothermal conditions and fully structural characterized by elemental analysis, IR, and single‐crystal X‐ray crystallography. Their thermal stability and photoluminescence properties were further investigated by TG‐DTA and fluorescence spectra. In both complexes, the adjacent metal ions (CdII for 1 and CoII for 2 ) are linked together by dicarboxylate groups of bqdc dianions in chelating bidentate and monodentate modes, respectively, generating a zigzag chain for 1 and linear chain for 2 . The relatively higher thermal stability up to 324 °C for 1 and strong fluorescence emissions jointly suggest that they are good candidates for luminescent materials. 相似文献
Two new layered complexes with the formulas of {[Cu(H2O)(HL)2Cl](NO3)}n ( 1 ) and {[Cu(H2O)2(HL)2](NO3)2}n ( 2 ) were solvothermally synthesized by the reactions of the bulky conjugated 4′‐(4‐hydroxyphenyl)‐4,2′:6′,4′′‐terpyridine ligand (HL) with different CuII salts, which were further used as photocatalysts to achieve hydrogen production from water splitting. Single‐crystal structural analyses reveal that both complexes feature coplanar (4 4) layers with different connection manners between the HL extended Z‐shaped chains. More interestingly, 1 possessing more negative conduction band potential and higher structural stability exhibits a large hydrogen production rate of 2.43 mmol · g–1 · h–1, which is four times higher than that of 2 . Thus, the CuII‐based coordination polymers modified by the bulky conjugated organic ligand can become potentially promising non‐Pt photocatalysts for hydrogen production from water splitting. 相似文献