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NNSFC [20901064, 20825103, 21021061, 21071119, 90922031]; Foundation for the Author of National Excellent Doctoral Dissertation of China [201219]; Ministry of Science and Technology of China [2012CB821704]

A discrete dihalide–decahydrate cluster of [X2(H2O)10]2– has been observed in a solid-state structure of {[Na2(H2O)6(H2O@TMEQ[6])]·2(C6H5NO3)}X2(H2O)10} (TMEQ[6] = α,α′,δ,δ′-tetramethylcucurbit[6]uril; X = Cl (1), Br (2)). Its structure can be viewed as a connection of two [X(H2O)3]− clusters with a uudd water tetramer through hydrogen-bonding interactions.

The use of 1-(4-pyridylmethyl)-2-methylimidazole (pmmid) combined with four kinds of benzenecarboxylic acid ligands has allowed the rational design of four novel Cd(II) coordination polymers (CPs), {[Cd(pmmid)(pa)(H2O)]·H2O}n (1), [Cd2(pmmid)2(cba)4] (2), [Cd1.5(pmmid)(tbba)3]n (3), and {[Cd(pmmid)(pma)0.5(H2O)]·5H2O}n (4), [H2pa = phthalic acid, Hcba = 4-chlorobenzoic acid, Htbba = 4-tert-butylbenzoic acid, and H4pma = pyromellitic acid], which were synthesized by reactions of Cd(OAc)2·2H2O and pmmid with aromatic acid under the ammoniacal condition and characterized by elemental analysis, infrared (IR) spectroscopy, powder X-ray diffraction (PXRD), and single crystal X-ray diffraction. Complex 1 possesses a one-dimensional (1D) chain architecture, complex 2 is an interesting 1D structure containing two kinds of 1D chains, complex 3 features a two-dimensional 63 topological network structure, and complex 4 is a novel three-dimensional coordination architecture framework containing a T4(2)10(2) water tape...

Five coordination compounds (CCs) of the formulas {[Ag(m-abn)2]·NO3}n (1), {[Ag2(m-abn)6]·(ClO4)2} (2), {[Ag(o-abn)2]·NO3}n (3), [Ag(o-abn)2(NO2)]n (4), and {[Ag(o-abn)2]·PF6}n (5) (m-abn = 3-aminobenzonitrile, and o-abn = 2-aminobenzonitrile) were synthesized and structurally characterized by element analysis, IR, powder X-ray diffraction, and X-ray single-crystal diffraction. Structural analysis reveals that aminobenzonitrile acts as bidentate μ2-N,N′ or monodentate μ1-N ligands in 1–5. Complex 1 is a 1D chain comprised of C2-symmetric [Ag(m-abn)]2 14-membered rings. The uncoordinated NO3– anions interact with the 1D chain to form a resulting 2D supramolecular sheet through N–O···N hydrogen bond. Complex 2 is a discrete binuclear Ag(I) CC incorporating concurrent bidentate μ2-N,N′ and monodentate μ1-N m-abn ligands. The variation of anions from NO3– to ClO4– results in the dimensionalities of 1 and 2 decreasing from 1D to 0D. When using o-abn, complexes 3–5 are obtained as 1D chain with C2-symmetric [Ag...

Two new mixed-ligand Zn(II) coordination polymers, namely, [Zn(bime)(glu)·4H2O]n (1) and [Zn(bime)(sub)·3H2O]n (2) (bime = 1,2-bis(imidazol-1′-yl)ethane, H2glu = glutaric acid, H2sub = suberic acid), have been synthesized and structurally characterized. Complex 1 exhibits a wavy two-dimensional (2D) sheet with (4,4) topology. Complex 2 is a three-dimensional (3D) framework with 5-fold interpenetrated diamond topology. Of particular interest, a discrete octamer water cluster comprised of a chairlike hexamer water cluster with two extra water molecules dangling on two diagonally vertices of the chair was observed in the grid of the 2D sheet of 1. In 2, a 1D infinite T5(2) water tape constructed from edge-sharing pentamer water clusters accommodates in the channels of the 3D network. The results suggest that the dicarboxylates play crucial roles in the formation of the different host structures as well as different guest water aggregations. Additionally, the thermal stabilities and photoluminescence spectra ...

A novel triple helix based on proton-transferred sebacic acid was observed in a 1:1 organic salt of [(Hambtz)+(Hsba)−·2H2O] (1, ambtz = 2-amino-6-methoxybenzothiazole, H2sba = sebacic acid) incorporating a zigzag water chain. Changing the solvent system, another simple 1D zigzag chain, cocrystal [(ambtz)2(H2sba)] (2), was obtained. The structural dissimilarity between them was dependent on different conformations of ambtz and H2sba modulated by solvent systems. The photoluminescence behaviors of 1 and 2 were also discussed.

The ultrasonic reactions of Ag2O with benzoguanamine and ancillary carboxylate ligands under the ammoniacal condition gave eight new coordination compounds (CCs), namely, [Ag4(bga)6(mal)2] (1), [Ag4(bga)6(mlc)2] (2), [Ag(bga)2(tpa)0.5]n (3), {[Ag(bga)(suc)0.5]·C2H5OH}n (4), {[Ag(bga)(pta)0.5]·CH3OH}n (5), {[Ag(bga)(ox)0.5]·C2H5OH·H2O}n (6), {[Ag2(bga)2(dnb)2]·DMF}n (7), and [Ag2(bga)2(pma)0.5(H2O)]n (8) (bga = benzoguanamine, H2mal = malonic acid, H2mlc = maleic acid, H2tpa = terephthalic acid, H2suc = succinic acid, H2pta = phthalic acid, H2ox = oxalic acid, Hdnb = 3,5-dinitrobenzoic acid, H4pma = pyromellitic acid, and DMF = N,N′-dimethylformamide). All CCs have been characterized by elemental analyses, IR spectra, and single-crystal X-ray diffraction. Compounds 1 and 2 are 0D discrete molecules and contain centrosymmetric [Ag2(mal)]2 and [Ag2(mlc)]2 units, respectively, which are extended to 1D supramolecular chains through intermolecule N–H···N complementary hydrogen bonds. Compounds 3 and 4 contain s...

A novel infinite 2D silver(I) phthalate coordination polymer (CP), {CH3CN⊂[Ag2(pta)]4·CH3CN}n, (1, H2pta = phthalic acid) was synthesized and characterized. The flowerpot-shaped cavity in the sheet accommodates a linear acetonitrile molecule through quadruplex Ag···Nacetonitrile interaction. Using H2O as a solvent in the same preparative procedure, another silver(I) phthalate CP 2, {[Ag2(pta)(H2O)]}n, was isolated. Complex 2 is also a 2D sheet but does not include any solvent-occupied cavity. A comparative experiment shows that the acetonitrile acts as a template for the sheet formation. Moreover, the TGA and photoluminescence spectra of 1 and 2 were discussed.

Two mixed-ligand Ag(I) coordination polymers (CPs), [Ag2(bpp)2(suc)·12H2O]n (1) and [Ag2(bpe)2(suc)·9H2O]n (2) (where bpp = 1,3-bis(4-pyridyl)propane, bpe = 1,3-bis(4-pyridyl)ethane, and H2suc = succinic acid), have been synthesized and structurally characterized. Both structures consist of cationic layers with Ag···π interacted chains of alternating metal and bis(pyridyl) ligands. The noncoordinated succinate (suc2−) in 1 or 2 serves as an anionic template driving surrounding water molecules to aggregate into an ordered 2D water-suc anionic layer. The interlamellar anions and cationic layers are stacked through weak electrostatic interaction and hydrogen bonds. One novel 1D water chain constructed from alternating water tetramer with uudd configuration and rare octamer exists in the anionic layer of 1. Each octameric water cluster consists of a pair of fused hexameric water clusters, and each water hexamer assumes a rare bag-shaped conformation. A discrete spirocyclic nonameric water cluster featuring tw...

National Natural Science Foundation of China [20721001]; MSTC [2007CB815301]; The National Science Fund of China for Fostering Talents in Basic Science [J0630429]

A series of new metal−organic frameworks, namely, [Ag(mapym)(suc)0.5·0.5H2O]n (1), [Ag2(mapym)2(glu)·1.5H2O]n (2), [Ag2(mapym)2(ipa)·2H2O]n (3), [Ag2(mapym)2(tpa)(H2O)]n (4), [Ag(dmapym)2(ox)0.5·H2O] (5), and [Ag(dmapym)(bbdc)0.5·0.5H2O]n (6) (mapym = 2-amino-4-methylpyrimidine, dmapym = 2-amino-4,6-dimethylpyrimidine, H2suc = succinic acid, H2glu = glutaric acid, H2ipa = isophthalic acid, H2tpa = terephthalic acid, H2ox = oxalic acid, H2bbdc = 4,4-bibenzenedicarboxylic acid), have been synthesized and structurally characterized. Complexes 1 and 2 exhibit two-dimensional (2D) interpenetrated and double-sheet structures, respectively. Complex 3 is a three-dimensional (3D) framework constructed through unusual 2D → 3D parallel interpenetration of a corrugated 2D 44-sql net. Complex 5 is a 0-dimensional (0D) H-shaped molecule, and the self-complementary N−H···N hydrogen bonds incorporating R44(14) hydrogen bond motifs extend these molecules into a 3D supramolecular framework. Complexes 4 and 6 are also 2D sh...

Two supramolecular architectures were assembled from the supermolecular building blocks of calixarenes and cucurbiturils through noncovalent binding. They not only exhibit an intriguing topology but also show clearly the role of hydrophobic−hydrophobic and hydrophilic−hydrophilic interactions in directing the supramolecular assembly.

Five Cu(II)/benzoate/4,4‘-bipy complexes, namely, [Cu(H2O)(benzoate)2(4,4‘-bipy)2](benzoic acid)2·(4,4‘-bipy) (1), [Cu2(H2O)2(benzoate)4(4,4‘-bipy)3]·(H2O)9 (2), [Cu2(benzoate)4(4,4‘-bipy)3] (3), [Cu3(H2O)4(benzoate)6(4,4‘-bipy)4.5]·(4,4‘-bipy)·(H2O)5 (4), and [Cu3(OH)2(H2O)2(benzoate)4(4,4‘-bipy)2] (5) (4,4‘-bipy = 4,4‘-bipyridine), have been synthesized through hydrothermal reaction of copper(II) nitrate, benzoic acid, and 4,4‘-bipyridine under different pH conditions. The diverse product structures show the marked sensitivity of the structural chemistry of the aromatic carboxylate ligand to synthesis conditions. Complex 1, which exhibits a zero-dimensional (0D) structure of mononuclear copper(II), is formed at pH = 5.5. At pH = 6.0, dimeric copper(II) complexes of 2 and 3 are formed. Reaction at pH = 7 leads to a one-dimensional (1D) structure of 4. A further increase of the pH to 8.0 results in a two-dimensional (2D) structure of 5. Crystal data are monoclinic, space group P2/n, a = 13.992(4) A, b = 5...

Solvothermal reactions of Cu(NO3)2·3H2O with trimesic acid (H3BTC) at different pH conditions yield two coordination polymers of [Cu3(BTC)2(H2O)3(NH3)4]n·2nH2O (1) and [Cu4(BTC)2(OH)2(H2O)2(NH3)4]n (2). Crystal structural analysis reveals that complex 1 exhibits a three-fold parallel interpenetration network and complex 2 shows a two-dimensional bilayer structure. Crystal data are orthorhombic, space group Pbcn, a = 11.242(3) A, b = 16.963(4) A, c = 13.898(4) A, Z = 4 for 1 and monoclinic, space group C2/c, a = 18.887(4) A, b = 10.761(2) A, c = 14.488(3) A, β = 126.100(3)°, Z = 4 for 2.

Four barrel-shaped artificial molecular capsules based on cucurbit[5]uril, [K4(C30H30N20O10)2(HCONH2)2(H2O)2Cl2]Cl2·CH3OH·17.5H2O (1), {[Ba2(C30H30N20O10)Cl](NO3)(H2O)5}Cl2·2H2O (2), [Cd(C30H30N20O10)Cl2](H3O)22+CdCl42-·2CH3OH2·4H2O (3), and {[La(C30H30N20O10)Cl]LaCl(H2O)9}Cl4·HCl·7H2O (4) were synthesized and structurally characterized by single-crystal X-ray diffractions. The crystal structure of these compounds show that chlorine anions were encapsulated in cucurbit[5]uril to form open or closed molecular capsules. 1 forms a novel one-dimensional (1D) polycationic chain in the solid state and the other three molecular capsules crystallize in isolated molecules.

Five Keggin-based metal complexes, [Ag3(2,4‘-bipy)3PMo12O40] (1), [Ag4(2,4‘-bipy)4SiW12O40] (2), [Ag3(2,4‘-bipy)4PW12O40] (3), [Cu4(2,4‘-bipy)4SiW12O40] (4), and [Cu3(2,4‘-bipy)4PW12O40] (5) (2,4‘-bipy = 2,4‘-bipyridine), were synthesized and structurally characterized. Among them, complexes 1, 2, and 4 show a cyclic structure, while complexes 3 and 5 exhibit a one-dimensional (1D) chain structure. Investigation of their structural differences reveals that anions play a key role in the formation of a cyclic structure.

A crownlike nonamer water cluster has been observed in the heterometallic supramolecular complex {[Cu(eda)2(H2O)2]3·[Ag6(mna)6]·9H2O} (1), which is built from one anionic hexanuclear silver cluster [Ag6(mna)6]6− and three mononulear [Cu(eda)2(H2O)2]2+ cations (H2mna = 2-mercaptonicotinic acid, eda = ethylenediamine). Moreover, the thermogravimetric curve, UV−vis absorption, and photoluminescence spectra of 1 were discussed.