A functionalised fullerene incorporating a double-chelating group binds transition metal cations and acts as an effective vehicle for delivering metals into carbon nanotubes.

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

Stack them up! AgI ions combined with functionalized fullerenes (C60) form either discrete binuclear metallacycles or extended polymeric networks (see structure), depending on the geometry of the functional groups on the fullerene and conditions of assembly, such as choice of solvent. Supporting information for this article is available on the WWW under http://www.wiley-vch.de/contents/jc_2002/2007/z700769_s.pdf or from the author. Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article.

A mild and one-pot protocol for the efficient and stereoselective synthesis of 1,2-trans-aldosyl mercaptans is presented.

Six new zinc phosphite hybrids are prepared under a variety of reaction conditions from the primary building blocks, trimethylenedipyridine, zinc acetate, and phosphorous acid. Neutral guest molecules are incorporated into several of the structures. Under hydrothermal conditions at 130 degrees C, an anionic framework structure, 1, templated on trimethylenedipyridinium, is obtained while a neutral ladder structure, 2, is formed at room temperature. These reactions are done at an initial pH of 4.7-5.0. When the reaction is done at an initial pH of 7.8-8.0, a neutral layered motif is obtained with 1,3-dipyridylpropane pillars and neutral guests in the interstitial space. Structures with water, phenol, and catechol as the guests, compounds 3, 4, and 5, respectively, are reported. The use of catechol as a template results in the breakup of the ZnPO sheet structure common to both 3 and 4. When amino acids, including alanine, were added to the reaction medium, a neutral three-dimensional framework, 6, is obtained with no incorporation of the potential template. The syntheses and structures of these new materials are reported.

Seven new cobalt(II) phosphites, [Co(HPO(3))(C(14)H(14)N(4))(H(2)O)(2)].2H(2)O (1), [Co(HPO(3))(C(22)H(18)N(4))].H(2)O (2), [Co(2)(HPO(3))(2)(C(22)H(18)N(4))(2)H(2)O].H(2)O (3), [Co(2)(HPO(3))(2)(C(12)H(10)N(4))(1.5)H(2)O].1.5H(2)O (4), [Co(HPO(3))(C(14)H(14)N(4))(0.5)].H(2)O (5), [Co(HPO(3))(C(18)H(16)N(4))(0.5)] (6), and [Co(HPO(3))(C(18)H(16)N(4))(0.5)] (7) were synthesized in the presence of 1,2-bis(imidazol-1-ylmethyl)benzene (L1), 1,4-bis(benzimidazol-1-ylmethyl)benzene (L2), 1,3-bis(benzimidazol-1-ylmethyl)benzene (L3), 1,4-bis(1-imidazolyl)benzene (L4), 1,4-bis(imidazol-1-ylmethyl)benzene (L5), 1,4-bis(imidazol-1-ylmethyl)naphthalene (L6), and 1,5-bis(imidazol-1-ylmethyl)naphthalene (L7), respectively, and their structures were determined by X-ray crystallography. Compound 1 is a molecular compound in which two cobalt(II) ions are held together by double mu-O linkages. The inorganic framework of compounds 2 and 3 are composed of vertex-shared CoO(2)N(2)/CoO(3)N(2) and HPO(3) polyhedra that form four rings; these are further linked by an organic ligand to generate 2D sheets. Compounds 4 and 5 both have 1D inorganic structures, with the bifunctional ligands connected to each side of the ladder by coordination bonds to give 2D hybrid sheets. A 3D organically pillared hybrid framework is observed in 6 and 7. In 6, the stacking of the interlayer pillars gives rise to a small hydrophobic channel that extends through the entire structure parallel to the sheets. The temperature-dependent magnetic susceptibility measurements of these compounds show weak interactions between the metal centers, mediated through the mu-O and/or O-P-O linkages.

The syntheses and structures of five new zinc phosphites [Zn(HPO(3))(C(4)H(6)N(2))] (1), [Zn(2)(HPO(3))(2)(C(10)H(10)N(2))(2)](2) (2), [Zn(HPO(3))(C(14)H(14)N(4))(0.5)] (3), [Zn(2)(HPO(3))(2)(C(14)H(14)N(4))].0.4H(2)O (4), and [Zn(2)(HPO(3))(2)(C(14)H(14)N(4))] (5) are reported. In compounds 1-3, the zinc atoms are ligated by 1-methylimidazole, 1-benzylimidazole, and 1,4-bis(imidazol-1-ylmethyl)benzene, respectively, while compounds 4 and 5 are synthesized in the presence of the same bifunctional ligand, 1,3-bis(imidazol-1-ylmethyl)benzene. The inorganic framework of compound 1 is composed of vertex-shared ZnO(3)N and HPO(3) tetrahedra that form 4-rings, which, in turn, are linked to generate a one-dimensional ladder structure. In 2, the inorganic framework is composed of 4-rings and 8-rings to form the well-known 4.8(2) 2D network. This is connected via C-H...pi interactions between 1-benzylimidazole ligand to generate a pseudo-pillared-layer structure. In 3, the inorganic framework again has the 4.8(2) topology pillared by the bis(imidazole) ligand, 1,3-bis(imidazol-1-ylmethyl)benzene. In 4, a new layer pattern is observed. Specifically, three edge-sharing 4-rings form triple-fused 4-rings. These tertiary building units are further connected to form 12-rings. The alternating triple 4-rings and 12-rings form a previously unknown 2D inorganic sheet. The sheets are joined together by the bis(imidazole) ligand, 1,3-bis(imidazol-1-ylmethyl)benzene, to generate a 3D pillared-layer structure. In 4, benzene rings and imidazole rings stack in a zigzag pattern in the interlayer space. A significant role for the triple 4-ring tertiary building unit in the formation of hybrid inorganic/organic metal phosphite structures is proposed for 4 and 5. In 5, the triple 4-rings fuse to give a 1D stair-step structure. Calculations show that the triple 4-ring pattern observed in the linear ladder structure of 1 is more stable than that in the stair step pattern of 5.

Six new zinc phosphates [C18H20N4][Zn4(HPO4)4(H2PO4)2(C18H18N4)3].2H2O (1), [Zn4(HPO4)4(C18H18N4)3].4H2O (2), [Zn3(HPO4)3(H2PO4)(C22H22N8)0.5(C22H24N8)0.5] (3), [Zn2(HPO4)2(C18H16N4)] (4), [Zn(HPO4)(C18H14N2)] (5), and [Zn2(HPO4)2(C12H10N4)] (6) have been synthesized under mild hydrothermal conditions in the presence of 1,4-bis(N-benzimidazolyl)butane (L1), 1,2,4,5-tetrakis(imidazol-1-ylmethyl)benzene (L2), 1,4-bis(imidazol-1-ylmethyl)naphthalene (L3), 9-(imidazol-1-ylmethyl)anthracene (L4), and 1,4-bis(1-imidazolyl)benzene (L5), respectively, and their structures were determined by X-ray crystallography. Compound 1 exhibits a unique inorganic motif of isolated 8-rings interconnected by L1. Compound 2, also formed from L1, contains a previously unobserved chain structure composed of edge-sharing 4-rings and 8-rings. Compound 3, prepared from L2, possesses an unusual one-dimensional framework, which is composed of vertex-sharing 4-rings and triple fused 4-rings. The inorganic portions of 4, 5, and 6 each adopt a layer structure. The sheets in 4 and 5 have a 4.8(2) topology, and in 6, a 6(3) topology is observed. The zinc atoms in compounds 1-6 are all tetrahedrally coordinated by a combination of phosphate groups and organic ligands. Potential relationships between the inorganic motifs reported in the present study are identified. These are indicative of a possible pattern of self-assembly of zinc and phosphorus tetrahedra and indicative of the role of the organic ligands in the formation of hybrid structures.

Two novel metal-organic frameworks (MOFs)--[Mn(titmb)(N3)2] x 1.5H2O (1) and [Mn3(titmb)2(C2O4)3(H2O)] x 10H2O (2)--were obtained by reactions of the flexible tripodal ligand 1,3,5-tris(imidazol-1-ylmethyl)-2,4,6-trimethylbenzene (titmb) with Mn(OAc)2 x 4H2O, together with NaN3 and K2C2O4, respectively. The structures of these MOFs were established by single-crystal X-ray diffraction analysis. The crystal data for 1 were as follows: monoclinic, C2/c, a = 20.956(13) A, b = 9.884(6) A, c = 24.318(14) A, beta = 95.87(5) degrees, Z = 8. The crystal data for 2 were as follows: triclinic, P1, a = 12.400(9) A, b = 16.827(12) A, c = 17.196(11) A, alpha = 66.35(5), beta = 95.87(5) degrees, gamma = 71.03(6), Z = 2. Complex 1 is a novel noninterpenetrating three-dimensional (3D) framework, in which the azide ligand connects Mn(II) atoms in an end-to-end (EE) mode to give [Mn-N-N-N-]n infinite one-dimensional (1D) chains, and complex 2 has a two-dimensional (2D) network structure in which the Mn(II) ions are linked by the oxalate anions to form 1D [Mn(C2O4)]n chains. Each titmb in these two complexes connects three metal atoms and serves as a three-connecting ligand. The magnetic properties of 1 and 2 were investigated. The results showed that the antiferromagnetic interactions occurred between the Mn(II) ions linked by the azide ligands in complex 1, and those linked by the oxalate anions and the carboxylate in syn-anti coordination mode in complex 2. The entirely different structures of complexes 1 and 2, on one hand, indicate that the azide and the oxalate ligands affected the structures of MOFs greatly, and on the other hand, reveals the potential applications of MOFs with the azide and oxalate ligands, which are efficient magnetic couplers.

A unique cationic zinc phosphate cluster linked by neutral bifunctional rigid ligands to form a two dimensional framework was synthesized and structurally characterized.

Four new zinc phosphates [Zn(HPO4)(C6H9N3O2)] (1), [Zn(HPO4)(C4H6N2)].H2O (2), [Zn2(HPO4)2(C14H14N4)].2H2O (3), and [Zn(HPO4)(C14H14N4)] (4) were synthesized in the presence of d-histidine, 1-methylimidazole, 1,4-bis(imidazol-1-ylmethyl)benzene (L1), and 1,2-bis(imidazol-1-ylmethyl)benzene (L2), respectively, and their structures were determined by X-ray crystallography. The inorganic framework of compounds 1, 2, and 3 is composed of vertex-shared ZnO3N and HPO4 tetrahedra that form four rings, which, in turn, are linked to generate a one-dimensional ladder structure. In 1 and 2 the organic groups (monoimidazole ligand) are located at each side of the ladders, while in 3 the bisimidazole ligand, 1,4-bis(imidazol-1-ylmethyl)benzene, links the ladders together to form a novel 2D structure. Compound 1 is the first zinc phosphate framework to be templated by an N-bonded chiral amino acid. In 4 the zero-dimensional four rings are joined together by the linear bridging ligand, 1,2-bis(imidazol-1-ylmethyl)benzene, to generate a one-dimensional framework with a new face-to-face structural motif. The 3D structure of compound 4 is stabilized by hydrogen-bonding, pi-pi interactions, and C-H...pi interactions. The approach of incorporating multifunctional ligands into zinc phosphate frameworks and linking the inorganic zinc phosphates subunits by an organic ligand provides opportunities for the design of new inorganic-organic open frameworks.

Three novel metal-organic frameworks (MOFs), [Cu(1)SO4].H2O (4), [Cu2(2)2(SO4)2].4H2O (5) and [Cu(3)(H2O)]SO4.5.5H2O (6), were obtained by hydrothermal reactions of CuSO4.5H2O with the corresponding ligands, which have different flexibility. The structures of the synthesized complexes were determined by single-crystal X-ray diffraction analyses. Complex 4 has a 2D network structure with two types of metallacycles. Complex 5 also has a 2D network structure in which each independent 2D sheet contains two sub-layers bridged by oxygen atoms of the sulfate anions. Complex 6 has a 2D puckered structure in which the sulfate anions serve as counter anions, which are different from those in complexes 4 (terminators) and 5 (bridges). The different structures of complexes 4, 5 and 6 indicate that the nature of organic ligands affected the structures of the assemblies greatly. The magnetic behavior of complex 5 and anion-exchange properties of complex 6 were investigated.

Two coordination polymers with M2L2 type metallocyclic rings [Mn(dimb)2(NCS)2]n (1) and [Mn(dimb)2(N3)2]n (2) were synthesized by reactions of bidentate ligand containing imidazole donors, namely 1,3-bis(imidazol-1-ylmethyl)-5-methylbenzene (dimb), with the manganese(II) salts. While the bimb ligand reacts with Zn(NO3)2⋅6H2O and NaN3 or AgClO4, complexes [Zn(dimb)2(N3)2]n (3) and {[Ag(dimb)]ClO4}n (4) with one-dimensional chain structure were obtained. When the ligand dimb reacted with Cu(NO3)2⋅3H2O, a two-dimensional network {[Cu(dimb)2(H2O)2](NO3)2}n (5) was achieved, in which the metal atoms had octahedral coordination geometry. The structures of these coordination complexes were determined by X-ray crystallography and the results revealed that both coordination geometry of metal atoms and conformation of ligand have great impacts on the structure of the supramolecular architectures. Magnetic properties of Mn(II) complexes were also investigated.

Six novel complexes, [Zn(IIMB)(4)(H2O)(2)](NO3)(2)(.)5H(2)O 1, {[Ag-2(IIMB)(2)][2,6-C10H6(COO)(2)]-6H(2)O](n) 2, {[Cu(IIMB)(2)]Br(2)(.)0.5H(2)O}(n) 3, {[Co(IIMB)(2)(SCN)(2)]}(n) 4, {[Cu(IIMB)(2)(SO4)](.)8.5H(2)O](n) 5, and {[Co(IIMB)(2)(H2O)(SO4)](4)(.) 29H(2)O](n) 6, were obtained by reactions of 1-(1-imidazolyl)-4-(imidazol-1-ylmethyl)benzene (IIMB) with the corresponding metal salts. X-ray diffraction analyses reveal that 1 is monomeric, in which IIMB acts as monodentate ligand, while the IIMB ligand in complexes 2-6 acts as bidentate ligand. Complex 2 has a single chain structure, while complexes 3 and 4 are double stranded chains. Complexes 5 and 6 display similar 2-D polycatenated architectures formed by the inclined interpenetration of 1-D double stranded chains. This kind of 1-D - 2-D inclined interpenetration has rarely been reported until now. In addition, the photoluminescence properties of the synthesized compounds were investigated in the solid state at room temperature.

Reactions of a new asymmetric ligand, 1-(1-imidazolyl)-4-(imidazol-1-ylmethyl)benzene (IIMB), with various metal [Cd(II), Mn(II), Zn(II)] salts led to the formation of molecular, one- (1D) and two-dimensional (2D) architectures [Cd(IIMB)2(H2O)(SO4)]·7.5H2O 1, [Cd(IIMB)2Cl2]·H2O 2, [Cd(IIMB)4(H2O)2](NO3)2·5H2O 3, [Cd(IIMB)(OAc)2]·H2O 4, [Mn(IIMB)2(SO4)(H2O)]·8.2H2O 5, [Mn(IIMB)4(H2O)2]Cl2·5H2O 6 and [Zn(IIMB)2]4(NO3)8·13.5H2O 7. All the structures were established by single-crystal X-ray diffraction analysis. Both compounds 1 and 5 with sulfate anion are 2D polycatenanes formed by the interlocking of 1D double-stranded chains, while 2 and 4 with chloride and acetate anions are 1D chains. The results provide nice examples of topologies of metal-organic frameworks controlled by the counter anions. Interestingly, 3 and 6 are discrete molecular complexes with monometallic cores and form 2D networks through strong intermolecular hydrogen bonds. Complex 7, obtained under the same conditions as 3, is a 1D tubular chain. The structural difference between 3 and 7 suggests the metal ions also have a significant effect on the construction of supramolecular architectures. Furthermore, the photoluminescence properties of these compounds were investigated in the solid state at room temperature.

Two coordination polymers [Ag(bib)]NO3.H2O (1) and [Ag(bib)]ClO4 (2) with one-dimensional (1D) chain structure were synthesized by reactions of ditopic ligand containing imidazole donors, namely, 1-bromo-3,5-bis(imidazol-1-ylmethyl)benzene (bib), with corresponding silver salts. While the bib ligand reacted with ditopic diacetato-zinc(II) acceptors, M2L2-type metallocyclic ring-like complex [Zn-2(bib)(2)(OAc)(4)].2H(2)O (OAc = acetate anion) (3) was obtained, which was further connected by Br...Br interactions to lead to the formation of 1D pseudo-polyrotaxane. When ligand bib reacted with Zn(NO3)(2).6H(2)O and Mn(NO3)(2), two complexes [Zn(bib)(2)(H2O)(2)](NO3)(2).2H(2)O (4) and [Mn(bib)(2)(H2O)(2)](NO3)(2).2H(2)O (5) with 2D network structure were obtained in which the metal atoms had octahedral coordination geometry. The structures of these coordination complexes were determined by X-ray crystallography, and the results revealed that the coordination geometry of metal atoms have a great impact on the structure of the supramolecular architectures. Furthermore, the nitrate anions located in the voids between the 2D cationic layers in 4 can be exchanged by nitrite anions, which means that complex 4 with 2D network structure has anion exchange properties.

Assembly of three-connecting ligands 1,3,5-tris(1-imidazolyl)benzene (tib) and 1,3,5-tris(imidazol-1-ylmethyl)-2,4,6-trimethylbenzene (titmb) with cadmium(II) and silver(I) salts provide new metal-organic frameworks, [Cd(tib)2](NO3)2·4H2O (1), [Ag(tib)(PPh3)](CF3SO3) (2) and [Ag(titmb)(PPh3)](CF3SO3)·1.5H2O (3) (PPh3=triphenylphosphine). Single-crystal X-ray diffraction studies reveal that complexes 1 and 3 are two-dimensional honeycomb networks, while complex 2 is a noninterpenetrated three-dimensional architecture with (10,3)-a topology. The results indicate that the nature (structure and flexibility) of the organic ligands and the bulky auxiliary ligand have great impact on the assembly and structure of metal-organic frameworks. The photoluminescent properties of the synthesized complexes were studied in the solid state at room temperature.

Four novel metal-organic frameworks (MOFs), [Cu(3)2](ClO4)2·0.67H2O (4), [Cu(3)2][Cu(mal)2]·6H2O (mal2− = −OCOCH2COO−) (5), [Cd(3)2](NO3)2·H2O, (6) and [Cd(3)(OAc)2]·6H2O (7), were obtained by self-assembly of the corresponding metal salts with a novel flexible tripodal ligand, 1-(1-imidazolyl)-3,5-bis(imidazol-1-ylmethyl)benzene (3), and their structures were determined by single crystal X-ray diffraction analyses. Complex 4 has a 2D network structure in which 3 shows two different coordination modes, one kind of 3 acts as a three-connecting ligand and the other one serves as a two-connecting (bridging) ligand using its two flexible arms. Complex 5 has an infinite 1D hinged chain structure in which only two of three imidazole groups of 3 are coordinated with the metal atoms while the last one is uncoordinated. In complexes 6 and 7, the metal centers are all six-coordinated; 6 has a 2D honeycomb and 7 has a 2D grid network structure, respectively. Ligand 3 has a trans conformation in 7, which is different from that in complexes 4 (cis and L-shaped), 5 (cis) and 6 (cis). The anion-exchange properties of complex 6 were investigated.