A homochiral luminescent 2D porous coordination polymer with collagen-type triple helices showing selective guest inclusion

A homochiral luminescent porous coordination polymer, [Cd(L)(H(2)O)]·3H(2)O, with interconnected collagen like triple-helical chains has been synthesized solvothermally by using cadmium(II) salt and a newly designed d-isosorbide-based, enantiomerically pure chiral ligand. The framework is a 2D porous material and forms a 1D channel along the a axis, with the channel dimensions ~6.2 × 4.4 ?(2). The compound has high selectivity in the uptake of water and methanol over other solvents (e.g., tetrahydrofuran, ethanol, benzene, and cyclohexane) inside the channels.     

Three novel organic-inorganic complexes based on decavanadate [V10O28]6- units: special water layers, open 3D frameworks and yellow/blue luminescences

Three unusual polyoxovanadate-based inorganic-organic hybrid complexes, [Zn(Im)(2)(DMF)(2)](2)[H(2)V(10)O(28)]·Im·DMF (1), [Zn(3)(Htrz)(6)(H(2)O)(6)][V(10)O(28)]·10H(2)O·Htrz (2) and {[Zn(3)(trz)(3)(H(2)O)(4)(DMF)](2)[V(10)O(28)]·4H(2)O}(n) (3) (Im = imidazole, Htrz = 1,2,4-triazole, DMF = N,N'-dimethylammonium) have been synthesized at room temperature via evaporative crystallization, and characterized by single-crystal X-ray diffraction. Complex 1 shows the structure of a discrete [V(10)O(28)](6-) cluster grafted by two [Zn(Im)(2)(DMF)(2)](2+) fragments through two bridged oxygen atoms, representing a rarely observed coordination mode. Complex 2 consists of a linear trinuclear Zn(II) unit bridging six Htrz ligands and a [V(10)O(28)](6-) cluster as the counter anion, where the extensive hydrogen-bonding interactions lead to {Zn(3)-V(10)}(SMF) and a special water layer involving (H(2)O)(36) rings, and consequently forms a unique 3D metal-organic-water supramolecular network. Complex 3 can be described as a 3,4-connected fsc-type network, and is the first example of open coordination 3D framework based on [V(10)O(28)](6-) and the other two different secondary building units, involving mononuclear and binuclear Zn(II)-Htrz motifs. The optical properties of complexes 1-3 in the solid state are investigated at room temperature. The results show that complexes 1 and 3 emit intense blue luminescences attributed to the ligands, while complex 2 exhibits an infrequent fluorescent property, emitting both blue and yellow luminescences at 472 and 603 nm simultaneously. Furthermore, powder X-ray diffraction and thermogravimetric analyses of 1-3 are also investigated, which demonstrate their high purities and thermal stabilities.     

Enhancing gas adsorption and separation capacity through ligand functionalization of microporous metal-organic framework structures

Hydroxyl- and amino- functionalized [Zn(BDC)(TED)(0.5)]·2DMF·0.2H(2)O leads to two new structures, [Zn(BDC-OH)(TED)(0.5)]·1.5DMF·0.3H(2)O and [Zn(BDC-NH(2))(TED)(0.5)]·xDMF·yH(2)O (BDC=terephthalic acid, TED=triethylenediamine, BDC-OH=2-hydroxylterephthalic acid, BDC-NH(2)=2-aminoterephthalic acid). Single-crystal X-ray diffraction and powder X-ray diffraction studies confirmed that the structures of both functionalized compounds are very similar to that of their parent structure. Compound [Zn(BDC)(TED)(0.5)]·2DMF·0.2H(2)O can be considered a 3D porous structure with three interlacing 1D channels, whereas both [Zn(BDC-OH)(TED)(0.5)]·1.5DMF·0.3H(2)O and [Zn(BDC-NH(2))(TED)(0.5)]·xDMF·yH(2)O contain only 1D open channels as a result of functionalization of the BDC ligand by the OH and NH(2) groups. A notable decrease in surface area and pore size is thus observed in both compounds. Consequently, [Zn(BDC)(TED)(0.5)]·2DMF·0.2H(2)O takes up the highest amount of H(2) at low temperatures. Interestingly, however, both [Zn(BDC-OH)(TED)(0.5)]·1.5DMF·0.3H(2)O and [Zn(BDC-NH(2))(TED)(0.5)]·xDMF·yH(2)O show significant enhancement in CO(2) uptake at room temperature, suggesting that the strong interactions between CO(2) and the functionalized ligands, indicating that surface chemistry, rather than porosity, plays a more important role in CO(2) adsorption. A comparison of single-component CO(2), CH(4), CO, N(2), and O(2) adsorption isotherms demonstrates that the adsorption selectivity of CO(2) over other small gases is considerably enhanced through functionalization of the frameworks. Infrared absorption spectroscopic measurements and theoretical calculations are also carried out to assess the effect of functional groups on CO(2) and H(2) adsorption potentials.     

Assembly and properties of transition-metal coordination polymers based on semi-rigid bis-pyridyl-bis-amide ligand: effect of polycarboxylates on the dimensionality

Seven new coordination polymers, [Co()(1,3-BDC)(H(2)O)(3)]·H(2)O (), [Co()(1,2-BDC)(H(2)O)]·H(2)O (), [Co(3)()(1,2,4-BTC)(2)(H(2)O)(4)]·4H(2)O (), [Co()(NPH)]·2H(2)O (), [Cu()(1,3-BDC)] (), [Cu()(1,2-BDC)] (), [Cu()(1,3,5-HBTC)(H(2)O)](2)·2H(2)O () ( = N,N'-bis(pyridin-3-yl)cyclohexane-1,4-dicarboxamide, 1,3-H(2)BDC = 1,3-benzenedicarboxylic acid, 1,2-H(2)BDC = 1,2-benzenedicarboxylic acid, 1,2,4-H(3)BTC = 1,2,4-benzenetricarboxylic acid, H(2)NPH = 3-nitrophthalic acid and 1,3,5-H(3)BTC = 1,3,5-benzenetricarboxylic acid) have been hydrothermally synthesized by assembling transition-metal cobalt-copper salts with semi-rigid bis-pyridyl-bis-amide ligand and different aromatic polycarboxylic acids. Complex exhibits a one-dimensional (1D) sinusoidal-like chain, which is further assembled into a three-dimensional (3D) supramolecular framework through hydrogen-bonding interactions. Complex possesses a 3D framework with 4-connected 6(6) topology, which contains a two-dimensional (2D) distorted asymmetric hexagonal grid. When 1,2,4-BTC is used in complex , a 3D framework with (6(3)·8(2)·10)(2)(6(5)·8)(2)(8) topology is constructed. Complex possesses a 3D framework with 4-connected 6(6) topology, which is similar to that of except for containing a 2D symmetric hexagonal grid. When Co(II) ion is replaced by Cu(II) ion, the 3D framework of complex with (4·6(2))(4·6(6)·8(3)) topology based on and 1,3-BDC ligands is obtained. Complex shows a 2D cross network consisting of a superposed Cu- 1D chain and 1,2-BDC, which is further expanded into a 3D supramolecular framework by hydrogen-bonding interactions. In complex , 1,3,5-HBTC is employed as the auxiliary ligand, and a 3D supramolecular framework based on the undulated 2D layers is formed through π-π stacking and hydrogen-bonding interactions. Both the metal ions and polycarboxylates play important roles in the construction of the title complexes. In addition, the electrochemical behaviors and the fluorescence properties of the seven complexes have been investigated.     

Solvent-induced single-crystal to single-crystal transformation of a 2D coordination network to a 3D metal-organic framework greatly enhances porosity and hydrogen uptake

Exposure to CH(2)Cl(2) at room temperature induces single-crystal to single-crystal transformation of the 2D coordination network [Zn(2)L(DMF)(4)]·2DMF·4H(2)O to the 3D metal-organic framework [Zn(2)L(H(2)O)(2)]·xsolv via dimerization of the metal-connecting points, leading to significant enhancement in framework stability, porosity, and H(2) uptake capacity.     

A metal-organic bilayer open framework with a dynamic component: single-crystal-to-single-crystal transformations

A metal-organic bilayered open framework, [Ni2(C26H52N10)]3[BTC]4.6C5H5N.36H2O (BOF-1, 1), has been prepared by the self-assembly of a new bismacrocyclic nickel(II) complex [Ni2(C26H52N10)(Cl)4].H2O (A) and sodium 1,3,5-benzenetricarboxylate (Na3BTC) in the mixture of water/DMSO/pyridine. The X-ray crystal structure of 1 shows that 2D layers with the cavities of brick-wall motifs (22.6 x 14.3 A2) are formed by the coordination of the nickel(II) complex with BTC3- ions and that the two 2D layers are linked with the p-xylyl bridging groups of the bismacrocycles as pillars to generate 3D channels in the bilayered framework. The voids of the channels occupy 61% of the total volume, which are filled with pyridine and water guest molecules. When 1 was dried at 75 degrees C for 1.5 h, [Ni2(C26H52N10)]3[BTC]4.4H2O (2) resulted by maintaining the single-crystallinity, which exhibited a dramatic decrease in the interlayer spacing as well as changes in the cell parameters. Solid 2 differentiates various alcohols such as MeOH, EtOH, isopropyl alcohol, and benzyl alcohol in toluene. When 1 was immersed in insoluble solvents such as pyridine and benzene, some guest molecules were exchanged with the aromatic molecules to give [Ni2(C26H52N10)]3[BTC]4.20pyridine.6H2O (3) and [Ni2(C26H52N10)]3[BTC]4.14benzene.19H2O (4), respectively. The guest-exchange processes also involve single-crystal-to-single-crystal transformation.     

Selective CO2 adsorption in a robust and water-stable porous coordination polymer with new network topology

A robust and water-stable porous coordination polymer [Cd(NDC)(0.5)(PCA)]·G(x) (1) (H(2)NDC = 2,6-napthalenedicarboxylic acid, HPCA = 4-pyridinecarboxylic acid, G = guest molecules) with new network topology has been synthesized solvothermally. The framework is 3D porous material and forms a 1D channel along the c-axis, with the channel dimensions ~9.48 × 7.83 ?(2). The compound has high selectivity in uptake of CO(2) over other gases (H(2), O(2), Ar, N(2), and CH(4)). The framework is highly stable in presence of water vapor even at 60 °C. The high CO(2) selectivity over other gases and water stability makes the compound promising candidate for industrial postcombustion gas separation application.     

Inorganic-organic hybrid compounds based on octamolybdates and metal-organic fragments with flexible multidentate ligand: syntheses, structures and characterization

Six polyoxometalate-based (POM) hybrid materials based on octamolybdate building blocks and metal-organic fragments with flexible multidentate ligand, namely [Cu(II)(2)(ttb)(2)(β-Mo(8)O(26))(H(2)O)(2)]·2H(2)O (1), Cu(I)(4)(ttb)(2)(β-Mo(8)O(26))(H(2)O) (2), [Cu(I)(4)(ttb)(3)(β-Mo(8)O(26))] (3), [Ni(2)(ttb)(2)(β-Mo(8)O(26))(H(2)O)(6)]·2H(2)O (4), [Zn(2)(ttb)(2)(α-Mo(8)O(26))(H(2)O)(2)] (5), and [Ag(4)(ttb)(2)(β-Mo(8)O(26))] (6), where ttb = 1,3,5-tris(1,2,4-triazol-1-ylmethyl)-2,4,6-trimethyl benzene, have been synthesized under hydrothermal conditions. Their structures have been determined by single-crystal X-ray diffraction analyses and further characterized by elemental analyses, TGA, IR spectra, and electrochemistry. Compounds 1 and 2 exhibit three-dimensional (3D) 2-fold interpenetrating frameworks with (3,6)-connected (4(1)·6(2))(4(2)·6(10)·10(3)) and (3,4)-connected (6(2)·8(1))(2)(6(2)·8(4)) topologies, respectively. We are not aware of any other examples of interpenetrating (3,6)- and (3,4)-connected frameworks which involves the octamolybdates. Compound 3 shows a rare two-dimensional (2D) 2-fold interpenetrating network structure. In compound 4, a 3D supramolecular framework with the channels is constructed by the hydrogen-bonding interactions between (β-Mo(8)O(26))(4-) polyanions and the Ni-ttb double layers, in which the guest (β-Mo(8)O(26))(4-) anions are included. If ZnO interactions are considered, the structure of 5 is a 3D (3,4)-connected framework with (4·8(2))(4·8(2)·10(3)) topology. In 6, the ttb ligand as a tetradentate ligand links the Ag atoms to yield a 2D POM-based network. By careful inspection of the structures of 1-6, it can be seen that the ttb ligand, the metal ion and the coordination mode of the octamolybdate anion play important roles in the formation of the POM-based MOFs.     

Hydrothermal synthesis, crystal structure and properties of Ag(I)-4f compounds based on 1H-benzimidazole-5,6-dicarboxylic acid

Seven novel heterometallic coordination polymers [CeAg(Hbidc)(2)(H(2)O)(2)] (1) and [LnAg(Hbidc)(2)]·3(H(2)O)[Ln = Sm (2), Gd (3), Tb (4), Dy (5), Ho (6), Er (7), H(3)bidc = 1H-benzimidazole-5,6-dicarboxylic acid] have been synthesized under hydrothermal conditions and characterized by elemental analysis, FT-IR, TG analysis, and single crystal X-ray diffraction. X-Ray analysis revealed that the seven complexes present two different types of three-dimensional (3D) structures. Complex 1 crystallized in an orthorhombic manner having a Pna2(1) space group, consisting of a 3D framework with a 1D heterometallic chain. Polymers 2-7 are isostructural and crystallized in an orthorhombic fashion having a Pccn space group existing of a two-fold interpenetrating 3D framework. The luminescence properties and the magnetic properties of all polymers were investigated.     

Mn(II) Coordination Polymers Based on Bi-, Tri-, and Tetranuclear and Polymeric Chain Building Units: Crystal Structures and Magnetic Properties

Five new Mn(II) coordination polymers, namely [Mn(2)(tbip)(2)(bix)] (1), [Mn(3)(tbip)(3)(bix)(2)] (2), [Mn(3)(tbip)(2)(Htbip)(2)(bib)(2)]·4H(2)O (3), [Mn(4)(tbip)(4)(bbp)(2)(H(2)O)(2)] (4), and [Mn(4)(tbip)(4)(bip)]·2H(2)O (5), were prepared by hydrothermal reactions of Mn(II) acetate with H(2)tbip (5-tert-butyl isophthalic acid) in the presence of different di-imidazolyl coligands (bix =1,4-bis(imidazol-1-ylmethyl)benzene, bib =1,4-bis(imidazol) butane, bbp =1,3-bis(benzimidazol)propane, bip =1,3-bis(imidazol)propane). All complexes were characterized by elemental analysis, IR spectra, thermogravimetric analysis, single-crystal X-ray crystallography, and powder X-ray diffraction. Single crystal X-ray studies show that these coordination polymers contain homometallic clusters varying from dimeric, trimeric, and tetrameric motifs to polymeric chains depending upon the coligands used. Complex 1 has a 3D 6-connected polycatenane network with dinuclear [Mn(2)O(2)] secondary building units. Complex 2 possesses a 3D 8-connected structure with trinuclear [Mn(3)(COO)(6)] units. Complex 3 shows a 3D pcu net based on trinuclear [Mn(3)(COO)(6)] clusters as nodes. Complex 4 features a 3D 8-connected structure constructed from the distorted square-grid tetranuclear [Mn(4)(μ(2)-COO)(8)(μ(2)-H(2)O)] units. Complex 5 shows a 3D (4,5,6)-connected net containing 1D μ-O/μ-COO alternately bridged chains. Magnetic susceptibility measurements indicate that complexes 1 and 3-5 show weak antiferromagnetic interactions between the adjacent Mn(II) ions, whereas 2 is a three-spin center homometallic ferromagnetic system.     

Flexible eightfold interpenetrating diamondoid network generating 1D channels: selective binding with organic guests

An 8-fold interpenetrating diamondoid network, [Ni(cyclam)]2[TCM]. 2DMF x 10H2O, has been prepared by the self-assembly of a Ni-(II)cyclam macrocyclic complex and sodium tetrakis[4-(carboxyphenyl)-oxamethyl]methane in DMF/water. The network shows an unusual [4 + 4] mode of interpenetration, generating 1D channels of effective window size 6.7 A x 4.7 A. The network shows flexible behavior: it becomes nonporous on removal of the guest molecules occupying the channels, but the open structure is restored when the desolvated solid is immersed in the mixture of H2O/DMF (1:1, v/v) for 5 min. The desolvated host has different binding capacities for n-butanol, pyridine, and ethanol.     

两个三维柱层式Ce混合羧酸多孔金属-有机骨架配合物的合成、结构与磁性

采用水热法合成了两个新的混合羧酸铈多孔金属-有机骨架配合物[Ce2(fum)3 (H2O)4?(bdc)?(H2O)2]n（1）和[Ce2(suc)2(ox)(H2O)4?(H2O)4]n（2）,利用元素分析、红外光谱、热重分析和单晶X射线衍射对其组成和结构进行了表征,并通过磁性测量研究了其磁学性能. 单晶X射线衍射结果表明,配合物1和2均为三维柱层式多孔金属-有机骨架结构. 配合物1由Ce离子和富马酸（fumarate, fum）形成层,层与层之间再通过富马酸作为柱状配体支撑形成三维结构,并在层间的两个方向上形成相互交错的通道,未配位的中性对苯二甲酸分子（p-benzenedicarboxylate, bdc）和晶格水分子填充于孔道中. 与配合物1类似,配合物2由Ce离子和丁二酸（succinate, suc）形成层,层间通过草酸（oxalate, ox）作为柱状配体支撑形成三维结构,在层间的三个方向上具有相互交错的通道,晶格水分子填充于孔道中.     

Flexible porous coordination polymers constructed from 1,2-bis(4-pyridyl)hydrazine via solvothermal in situ reduction of 4,4'-azopyridine

Solvothermal reactions of Zn(NO(3))(2), 1,4-benzenedicarboxylic acid (H(2)bdc), and 4,4'-azopyridine (azpy) in different conditions yielded [Zn(bdc)(bphy)]·DMF·H(2)O (1a, bphy = 1,2-bis(4-pyridyl)hydrazine, DMF = N,N-dimethylformamide) and [Zn(bdc)(bphy)]·EtOH·H(2)O (1b) with two-fold interpenetrated dmp topology and [Zn(2)(bdc)(2)(bphy)]·1.5EtOH·H(2)O (2a) and [Zn(2)(bdc)(2)(bphy)]·DMA·1.5H(2)O (2b, DMA = N,N-dimethylacetamide) with two-fold interpenetrated pcu topology. The in situ reduction of azpy to bphy was confirmed by single-crystal structures and LC-MS analyses of the acid-digested crystalline samples, as well as controlled solvothermal experiments. Removal of the guest molecules in 1a/1b and 2a/2b converts the materials to guest-free phases [Zn(bdc)(bphy)] (1) and [Zn(2)(bdc)(2)(bphy)] (2), respectively, which were identified by PXRD. CO(2) sorption experiments performed at 195 and 298 K showed low porosity for 1 and gated sorption behavior for 2. At 298 K, 2 exhibits high selectivity for adsorbing CO(2) over CH(4).     

A 3D polar nanotubular coordination polymer with dynamic structural transformation and ferroelectric and nonlinear-optical properties

A chiral coordination nanotube, [Cd(3)(BPT)(2)(H(2)O)(9)]·2H(2)O (Cd-1; BPT = biphenyl-3,4',5-tricarboxylate), has been synthesized from achiral components and structurally characterized. It consists of homochiral channels based on right-handed helical chains and shows an interdigitated interaction to give a chiral 3D network. The chiral nanotubular framework exhibts dynamic structural transformation upon removal of the guest molecules, and the polarity of this compound induces it to display both ferroelectric and nonlinear-optical properties.     

Syntheses, structures, and magnetic properties of a family of tetra-, hexa-, and nonanuclear Mn/Ni heterometallic clusters

A family of Mn(III)/Ni(II) heterometallic clusters, [Mn(III)(4)Ni(II)(5)(OH)(4)(hmcH)(4)(pao)(8)Cl(2)]·5DMF (1·5DMF), [Mn(III)(3)Ni(II)(6)(N(3))(2)(pao)(10)(hmcH)(2)(OH)(4)]Br·2MeOH·9H(2)O (2·2MeOH·9H(2)O), [Mn(III)Ni(II)(5)(N(3))(4)(pao)(6)(paoH)(2)(OH)(2)](ClO(4))·MeOH·3H(2)O (3·MeOH·3H(2)O), and [Mn(III)(2)Ni(II)(2)(hmcH)(2)(pao)(4)(OMe)(2)(MeOH)(2)]·2H(2)O·6MeOH (4·2H(2)O·6MeOH) [paoH = pyridine-2-aldoxime, hmcH(3) = 2, 6-Bis(hydroxymethyl)-p-cresol], has been prepared by reactions of Mn(II) salts with [Ni(paoH)(2)Cl(2)], hmcH(3), and NEt(3) in the presence or absence of NaN(3) and characterized. Complex 1 has a Mn(III)(4)Ni(II)(5) topology which can be described as two corner-sharing [Mn(2)Ni(2)O(2)] butterfly units bridged to an outer Mn atom and a Ni atom through alkoxide groups. Complex 2 has a Mn(III)(3)Ni(II)(6) topology that is similar to that of 1 but with two corner-sharing [Mn(2)Ni(2)O(2)] units of 1 replaced with [Mn(3)NiO(2)] and [MnNi(3)O(2)] units as well as the outer Mn atom of 1 substituted by a Ni atom. 1 and 2 represent the largest 3d heterometal/oxime clusters and the biggest Mn(III)Ni(II) clusters discovered to date. Complex 3 possesses a [MnNi(5)(μ-N(3))(2)(μ-OH)(2)](9+) core, whose topology is observed for the first time in a discrete molecule. Careful examination of the structures of 1-3 indicates that the Mn/Ni ratios of the complexes are likely associated with the presence of the different coligands hmcH(2-) and/or N(3)(-). Complex 4 has a Mn(III)(2)Ni(II)(2) defective double-cubane topology. Variable-temperature, solid-state dc and ac magnetization studies were carried out on complexes 1-4. Fitting of the obtained M/(Nμ(B)) vs H/T data gave S = 5, g = 1.94, and D = -0.38 cm(-1) for 1 and S = 3, g = 2.05, and D = -0.86 cm(-1) for 3. The ground state for 2 was determined from ac data, which indicated an S = 5 ground state. For 4, the pairwise exchange interactions were determined by fitting the susceptibility data vs T based on a 3-J model. Complex 1 exhibits out-of-phase ac susceptibility signals, indicating it may be a SMM.     

Host-guest supramolecular interactions in the coordination compounds of 4,4'-azobis(pyridine) with MnX2 (X = NCS–, NCNCN–, and PF6(–)): structural analyses and theoretical study

Three new Mn(II) coordination compounds {[Mn(NCNCN)(2)(azpy)]·0.5azpy}(n) (1), {[Mn(NCS)(2)(azpy)(CH(3)OH)(2)]·azpy}(n) (2), and [Mn(azpy)(2)(H(2)O)(4)][Mn(azpy)(H(2)O)(5)]·4PF(6)·H(2)O·5.5azpy (3) (where azpy = 4,4'-azobis(pyridine)) have been synthesized by self-assembly of the primary ligands, dicyanamide, thiocyanate, and hexafluorophosphate, respectively, together with azpy as the secondary spacer. All three complexes were characterized by elemental analyses, IR spectroscopy, thermal analyses, and single crystal X-ray crystallography. The structural analyses reveal that complex 1 forms a two-dimensional (2D) grid sheet motif. These sheets assemble to form a microporous framework that incorporates coordination-free azpy by host-guest π···π and C-H···N hydrogen bonding interactions. Complex 2 features azpy bridged one-dimensional (1D) chains of centrosymmetric [Mn(NCS)(2)(CH (3)OH)(2)] units which form a 2D porous sheet via a CH(3)···π supramolecular interaction. A guest azpy molecule is incorporated within the pores by strong H-bonding interactions. Complex 3 affords a 0-D motif with two monomeric Mn(II) units in the asymmetric unit. There exist π···π, anion···π, and strong hydrogen bonding interactions between the azpy, water, and the anions. Density functional theory (DFT) calculations, at the M06/6-31+G* level of theory, are used to characterize a great variety of interactions that explicitly show the importance of host-guest supramolecular interactions for the stabilization of coordination compounds and creation of the fascinating three-dimensional (3D) architecture of the title compounds.     

Two novel Dy8 and Dy11 clusters with cubane [Dy4(μ3-OH)4]8+ units exhibiting slow magnetic relaxation behaviour

Two unique octa- and hendeca-nuclear dysprosium(III) clusters incorporating [Dy(4)(μ(3)-OH)(4)](8+) cubane units have been synthesized with the 1,10-phenanthroline-2,9-dicarbaldehyde dioxime (H(2)phendox) ligand and DyCl(3)·6H(2)O or Dy(OAc)(3)·4H(2)O. They are [Dy(8)(OH)(8)(phendox)(6)(H(2)O)(8)]Cl(2)(OH)(2)·18H(2)O·18MeOH (1) and [Dy(11)(OH)(11)(phendox)(6)(phenda)(3)(OAc)(3)](OH)·40H(2)O·7MeOH (2). Adjacent Dy(8) in 1 or Dy(11) in 2 motifs are packed by off-set π-π interactions of the aromatic rings on phendox(2-) to generate a 3D supramolecular architecture in the honeycomb topology and with 1D or 3D channels along the c-axis. Adsorption research shows that complex 1 has selective adsorption ability for H(2)O over small gas molecules (H(2), N(2), CO(2)). Complex 2 is stable upon the removal of guest molecules and the desolvated compound absorbed a considerable amount of CO(2). Furthermore, the oximes underwent hydrolysis to carboxylic acid and the resulting 1,10-phenanthroline-2,9-dicarboxylate link the dysprosium atoms to form a hendecanuclear cluster of 2. Magnetic studies reveal that both clusters exhibit slow magnetic relaxation behavior, expanding upon the recent reports of the pure 4f type single-molecule magnets (SMMs).     

A series of chiral coordination polymers containing helicals assembled from a new chiral (R)-2-(4'-(4'-carboxybenzyloxy)phenoxy)propanoic acid: syntheses, structures and photoluminescent properties

Ten new chiral coordination polymers, namely, [Ni(L)(H(2)O)(2)] (1), [Co(L)(H(2)O)(2)] (2), [Cd(L)(H(2)O)] (3), [Cd(L)(phen)] (4), [Mn(2)(L)(2) (phen)(2)]·H(2)O (5), [Cd(2)(L)(2)(biim-4)(2)] (6), [Zn(2)(L)(2)(biim-4)(2)] (7), [Cd(L)(pbib)] (8), [Cd(L)(bbtz)] (9) and [Cd(L)(biim-6)] (10), where phen = 1,10-phenathroline, biim-4 = 1,1'-(1,4-butanediyl)bis(imidazole), pbib = 1,4-bis(imidazole-1-ylmethyl)benzene, bbtz = 1,4-bis(1,2,4-triazol-1-ylmethyl)benzene, biim-6 = 1,1'-(1,6-hexanedidyl)bis(imidazole), and H(2)L = (R)-2-(4'-(4'-carboxybenzyloxy)phenoxy)propanoic acid, have been synthesized under hydrothermal conditions. Their structures have been determined by single-crystal X-ray diffraction analyses and further characterized by infrared spectra (IR), powder X-ray diffraction (PXRD), elemental analyses and thermogravimetric (TG) analyses. Compounds 1 and 2 exhibit similar 1D left-handed helical chains, which are further extended into 3D supramolecular structures through O-H···O hydrogen-bonding interactions, respectively. Compound 3 shows a 2D double-layer architecture containing helical chains. Compound 4 features two types of 2D undulated sheets with helical chains, which are stacked in an ABAB fashion along the c direction. Compound 5 possesses a 1D double chain ribbon structure containing unusual meso-helical chains, which is linked by π-π interactions into a 2D supramolecular layer. These layers are further extended by hydrogen-bonding interactions to form a 3D supramolecular assembly. Compounds 6 and 7 are isostructural and exhibit 2D (4(4))-sql networks with helical chains. Neighboring sheets are further linked by C-H···O hydrogen-bonding interactions to generate 3D supramolecular architectures. Compounds 8-10 are isostructural and display 3D 3-fold interpenetrating diamond frameworks with helical chains. The effects of coordination modes of L anions, metal ions and N-donor ligands on the structures of the coordination polymers have been discussed. The luminescent properties of 3, 4 and 6-10 have also been investigated in detail.     

Multifunctional fourfold interpenetrating diamondoid network: gas separation and fabrication of palladium nanoparticles

A fourfold interpenetrating diamondoid network, [{[Ni(cyclam)]2-(mtb)}(n)].8n H2O.4n DMF (1) (MTB=methanetetrabenzoate, DMF=dimethylformamide), has been assembled from [Ni(cyclam)][ClO4]2 (cyclam=1,4,8,11-tetraazacyclotetradecane) and methanetetrabenzoic acid (H4MTB) in DMF/H2O (7:3, v/v) in the presence of triethylamine (TEA). Despite the high-fold interpenetration, 1 generates 1D channels that are occupied by water and DMF guest molecules. Solid 1, after removal of guest molecules, exhibits selective gas adsorption behavior for H2, CO2, and O2 rather than N2 and CH4, suggesting possible applications in gas separation technologies. In addition, solid 1 can be applied in the fabrication of small Pd (2.0+/-0.6 nm) nanoparticles without any extra reducing or capping agent because a Ni II macrocyclic species incorporated in 1 reduces Pd II ions to Pd 0 on immersion of 1 in the solution of Pd(NO3)2.2H2O in MeCN at room temperature.     

New coordination polymers with extended arm cyclotriguaiacyclene ligands: 1D chains, and interpenetrating or polycatenating 2D (4(2).6(2))(4.6(2))2 networks

A series of new 1D chain and 2D coordination polymers with cyclotriguaiacylene-type ligands are reported. A zig-zag 1D coordination chain is found in complex [Cd(2)(4ph4py)(NO(3))(3)(H(2)O)(2)(DMA)(2)]·(NO(3))·(DMA)(4), where 4ph4py = tris[4-(4-pyridyl)benzoyl]-cyclotriguaiacylene and DMA = dimethylacetamide, while complex [Zn(4ph4py)(2)(CF(3)COO)(H(2)O)]·(CF(3)COO)(NMP)(7), where NMP = N-methylpyrrolidone, has a doubly bridged coordination chain structure. Complexes [M(3ph3py)(NO(3))(2)]·(NMP)(4) where M = Co or Zn, 3ph3py = tris[3-(3-pyridyl)benzoyl]cyclotriguaiacylene, are isostructural and feature 1D ladder coordination chains. Complexes [Cd(2)(4ph4py)(2)(NO(3))(4)(NMP)]·(NMP)(9)(H(2)O)(4) and [Co(4ph4py)(H(2)O)(2)]·(NO(3))(2)·(DMF)(2), where DMF = dimethylformamide, both have (3,4)-connected 2D coordination polymers with a rare (4(2).6(2))(4.6(2))(2) topology. A 2D coordination polymer with this topology is also found in complex [Co(2)(3ph4py)(2)(NO(3))(H(2)O)(5)]·(NO(3))(3)·(DMF)(9) where 3ph4py = tris[3-(4-pyridyl)benzoyl]cyclotriguaiacylene. All 2D coordination polymer complexes are interpenetrating or polycatenating. [Co(2)(3ph4py)(2)(NO(3))(H(2)O)(5)](3+)polymers form a 2D→3D polycatenation showing self-complementary "hand-shake" interactions between the host-type ligands.