1,2,4-Triazolyl-carboxylate-based MOFs incorporating triangular Cu(II)-hydroxo clusters: topological metamorphosis and magnetism.

Bifunctional 1,2,4-triazole-carboxylate ligands, an achiral 1,2,4-triazol-4-yl-acetic acid (trgly-H) and a chiral (d)-2-(1,2,4-triazol-4-yl)-propionic acid (d-trala-H), derived from the corresponding α-amino acid precursors revealed unique binding abilities in the construction of Cu(II)-coordination polymers composing discrete triangular [Cu3(μ3-OH)] clusters. A related series of MOFs, [Cu3(μ3-OH)(trgly)3(SO4)]·2H2O (1a), [Cu3(μ3-OH)(trgly)3(H2O)3]SO4·16H2O (1b), Cu3(μ3-OH)(d-trala)3(ClO4)0.5](ClO4)1.

Self-assembly cavitand precisely recognizing hexafluorosilicate: a concerted action of two coordination and twelve CH···F bonds.

Bis-pyridazine tectons support the structure of metallosupramolecular cavitand Cu2L4(4+), which is capable of selective encapsulation of SiF6(2-) anions by a set of multiple host-guest interactions.

Unprecedented trapping of difluorooctamolybdate anions within an α-polonium type coordination network.

New fluorinated hybrid solids [Mo2F2O5(tr2pr)] (1), [Co3(tr2pr)2(MoO4)2F2]·7H2O (2), and [Co3(H2O)2(tr2pr)3(Mo8O26F2)]·3H2O (3) (tr2pr = 1,3-bis(1,2,4-triazol-4-yl)propane) were prepared from the reaction systems consisting of Co(OAc)2/CoF2 and MoO3/(NH4)6Mo7O24, as Co(II) and Mo(VI) sources, in water (2) or in aqueous HF (1, 3) employing mild hydrothermal conditions. The tr2pr ligand serves as a conformationally flexible tetradentate donor. In complex 1, the octahedrally coordinated Mo atoms are linked in the discrete corner-sharing {Mo2(μ2-O)F2O4N4} unit in which a pair of tr-heterocycles (tr = 1,2,4-triazole) is arranged in cis-positions opposite to "molybdenyl" oxygen atoms.

Cobalt(II) and cadmium(II) square grids supported with 4,4'-bipyrazole and accommodating 3-carboxyadamantane-1-carboxylate.

In poly[[bis(μ-4,4'-bi-1H-pyrazole-κ(2)N(2):N(2'))bis(3-carboxyadamantane-1-carboxylato-κO(1))cobalt(II)] dihydrate], {[Co(C12H15O4)2(C6H6N4)2]·2H2O}n, (I), the Co(2+) cation lies on an inversion centre and the 4,4'-bipyrazole (4,4'-bpz) ligands are also situated across centres of inversion. In its non-isomorphous cadmium analogue, {[Cd(C12H15O4)2(C6H6N4)2]·2H2O}n, (II), the Cd(2+) cation lies on a twofold axis. In both compounds, the metal cations adopt an octahedral coordination, with four pyrazole N atoms in the equatorial plane [Co-N = 2.

Functionalized adamantane tectons used in the design of mixed-ligand copper(II) 1,2,4-triazolyl/carboxylate metal-organic frameworks.

Bistriazoles, 1,3-bis(1,2,4-triazol-4-yl)propane (tr(2)pr) and 1,3-bis(1,2,4-triazol-4-yl)adamantane (tr(2)ad), were examined in combination with the rigid tetratopic 1,3,5,7-adamantanetetracarboxylic acid (H(4)-adtc) platform for the construction of neutral heteroleptic copper(II) metal-organic frameworks. Two coordination polymers, [{Cu(4)(OH)(2)(H(2)O)(2)}{Cu(4)(OH)(2)}(tr(2)pr)(2)(H-adtc)(4)]·2H(2)O (1) and [Cu(4)(OH)(2)(tr(2)ad)(2)(H-adtc)(2)(H(2)O)(2)]·3H(2)O (2), were synthesized and structurally characterized. In complexes 1 and 2, the N(1),N(2)-1,2,4-triazolyl (tr) and μ(3)-OH(-) groups serve as complementary bridges between adjacent metal centers supporting the tetranuclear dihydroxo clusters.

1,2,4-Triazole functionalized adamantanes: a new library of polydentate tectons for designing structures of coordination polymers.

A series of functionalized adamantanes: 1,3-bis(1,2,4-triazol-4-yl)(tr(2)ad); 1,3,5-tris(1,2,4-triazol-4-yl)-(tr(3)ad); 1,3,5,7-tetrakis(1,2,4-triazol-4-yl)adamantanes (tr(4)ad) and 3,5,7-tris(1,2,4-triazol-4-yl)-1-azaadamantane (tr(3)ada) were developed as a new family of geometrically rigid polydentate tectons for supramolecular synthesis of framework solids. The coordination compounds were prepared under hydrothermal conditions; their structures reveal a special potential of the triazolyl adamantanes for the generation of highly-connected and open frameworks as well as structures based upon polynuclear metal clusters assembled with short-distance N(1),N(2)-triazole bridges. Complexes [Cd{L}(2)]A·nH(2)O [L = tr(3)ad, A = 2NO(3)(-) (4), CdCl(4)(2-) (5); L = tr(3)ada, A = CdI(4)(2-) (7)] are isomorphous and adopt a layered 3,6-connected structure of CdI(2) type.

Facile access to a series of large polycondensed pyridazines and their utility for the supramolecular synthesis of coordination polymers.

Domino cyclization of ketoenols and hydrazine leads to a series of polycondensed pyridazines, which reveal potential as rigid N-donor multidentate ligands for supramolecular synthesis of open coordination polymers.

Self-assembly hexanuclear metallacontainer hosting halogenated guest species and sustaining structure of 3D coordination framework.

Chloride-centered hexanuclear hydroxopyrazolate reveals potential as a receptor of halomethane and halometallate species and as a molecular building block for coordination polymers.

Cadmium(II) thio- and selenocyanate complexes of 3,3'-bis(1,2,4-triazol-4-yl)-1,1'-biadamantane, a ligand designed with an 'extended nanodiamond' aliphatic platform.

In the structures of the Cd(II) pseudohalide coordination polymer poly[[diaquabis[mu(2)-3,3'-bis(1,2,4-triazol-4-yl)-1,1'-biadamantane-kappa(2)N(1):N(1')]cadmium(II)] dithiocyanate dihydrate], {[Cd(C(24)H(32)N(6))(2)(H(2)O)(2)](NCS)(2).2H(2)O}(n), (I), and the isomorphous selenocyanate analogue, {[Cd(C(24)H(32)N(6))(2)(H(2)O)(2)](NCSe)(2).2H(2)O}(n), (II), the Cd(II) cations occupy inversion centres and have octahedral CdN(4)O(2) environments, completed by four N atoms of the organic ligands [Cd-N = 2.

The chiral auxiliary N-1-(1'-naphthyl)ethyl-O-tert-butylhydroxylamine: a chiral Weinreb amide equivalent.

The chiral auxiliary N-1-(1'-naphthyl)ethyl-O-tert-butylhydroxylamine is readily prepared from N-hydroxyphthalimide in four steps, with resolution giving access to both enantiomers in > 98% ee, on a multigram (> 25 g) scale. Conversion to a range of N-acyl derivatives, followed by highly diastereoselective alkylation (> or = 94% de) gives the corresponding chiral, 2-substituted derivatives as single diastereoisomers (> 98% de) after chromatography. Reductive cleavage with LiAlH(4) allows direct access to chiral aldehydes, and treatment with MeLi gives chiral methyl ketones in excellent enantiopurity (> or = 94% ee).

1,3,5-Triphenyladamantane and 1,3,5,7-tetraphenyladamantane.

In 1,3,5-triphenyladamantane, C(28)H(28), (I), and 1,3,5,7-tetraphenyladamantane, C(34)H(32), (II), the molecules possess symmetries 3 and 4, and are situated across threefold and fourfold improper axes, respectively. The molecules aggregate by means of extensive C-H..

1,2,4,5-tetrazine: an unprecedented micro4-coordination that enhances ability for anion pi interactions.

A series of framework coordination polymers reveals the use of 1,2,4,5-tetrazines as efficient bridging ligands towards silver(i) and copper(i) ions. All four nitrogen atoms were functional as lone pair donors leading to an unprecedented mu(4)-coordination of the ligands (1,2,4,5-tetrazine, ttz; 3,6-dimethyl-1,2,4,5-tetrazine, Me(2)ttz) in [Ag(ttz)(X)] (X = NO(3), ; ClO(4), ), [Ag(2)(Me(2)ttz)(NO(3))(2)] (), [Ag(2)(Me(2)ttz)(H(2)O)(2)(ClO(4))(2)] (), [Ag(3)(Me(2)ttz)(H(2)O)(2)(CF(3)SO(3))(3)] () and [Cu(4)Cl(4)(Me(2)ttz)] (). In and , micro(4)-tetrazines and silver ions (AgN(4), Ag-N 2.

Copper(II) bromide and copper(II) acetate complexes of 4,4'-(p-phenylene)bipyridazine.

4,4'-(p-Phenylene)bipyridazine, C(14)H(10)N(4), (I), and the coordination compounds catena-poly[[dibromidocopper(II)]-mu-4,4'-(p-phenylene)bipyridazine-kappa(2)N(2):N(2')], [CuBr(2)(C(14)H(10)N(4))](n), (II), and catena-poly[[[tetrakis(mu-acetato-kappa(2)O:O')dicopper(II)]-mu-4,4'-(p-phenylene)bipyridazine-kappa(2)N(1):N(1')] chloroform disolvate], {[Cu(2)(C(2)H(3)O(2))(4)(C(14)H(10)N(4))].2CHCl(3)}(n), (III), contain a new extended bitopic ligand. The combination of the p-phenylene spacer and the electron-deficient pyridazine rings precludes C-H.

Hydrate frameworks involving the pyridazino[4,5-d]pyridazine unit as a multiple hydrogen-bond acceptor.

1,4,5,8-Tetramethylpyridazino[4,5-d]pyridazine trihydrate, C(10)H(12)N(4) x 3 H(2)O, (I), and 1,2,3,6,7,8-hexahydrocinnolino[5,4,3-cde]cinnoline tetrahydrate, C(12)H(12)N(4) x 4 H(2)O, (II), exhibit exceptional functionality of the condensed N(4)-heteroaromatic frame as a symmetric acceptor of four hydrogen bonds [N...

Copper(II) and cadmium(II) isothiocyanate coordination polymers with 4,4'-bi-1,2,4-triazole.

The coordination polymers catena-poly[[[(4,4'-bi-1,2,4-triazole-kappaN(1))bis(thiocyanato-kappaN)copper(II)]-mu-4,4'-bi-1,2,4-triazole-kappa(2)N(1):N(1')] dihydrate], {[Cu(NCS)(2)(C(4)H(4)N(6))(2)].2H(2)O}(n), (I), and poly[tetrakis(mu-4,4'-bi-1,2,4-triazole-kappa(2)N(1):N(1'))bis(mu-thiocyanato-kappa(2)N:S)tetrakis(thiocyanato-kappaN)tricadmium(II)], [Cd(3)(NCS)(6)(C(4)H(4)N(6))(4)](n), (II), exhibit chain and two-dimensional layer structures, respectively. The differentiation of the Lewis acidic nature of Cu(II) and Cd(II) has an influence on the coordination modes of the triazole and thiocyanate ligands, leading to topologically different polymeric motifs.

Silver(I) ions bridged by pyridazine: doubling the ligand functionality for the design of unusual 3D coordination frameworks.

Nitrogen donor tetradentate ligands 4,4'-bipyridazine (bpdz) and pyridazino[4,5-d]pyridazine (pp) were prepared by inverse electron demand Diels-Alder cycloaddition reactions of 1,2,4,5-tetrazine. Examination of their behaviour towards silver(I) ions revealed a special potential of the ligands for the design of 3D coordination frameworks involving characteristic polynuclear and polymeric silver(I)-pyridazine motifs and multiple coordination of the ligands. Ag4(pp)5(ClO4)4 and Ag4(pp)5(SiF6)(BF4)(2).

4,4'-Bipyridazine: a new twist for the synthesis of coordination polymers.

A new polydentate ligand 4,4'-bipyridazine (4,4'-bpdz) was prepared by employing inverse electron demand cycloaddition of 1,2,4,5-tetrazine. A unique combination of structural simplicity, ampolydentate character and efficient donor properties towards Cu(I), Cu(II) and Zn(II) provide wide new possibilities for the synthesis of coordination polymers incorporating the 4,4'-bpdz module either as a bi-, tri- or tetradentate connector between the metal ions. 1D coordination polymers Cu(2)(4,4'-bpdz)(CH(3)CO(2))(4) x 4H(2)O and Zn(4,4'-bpdz)(NO(3))(2), and interpenetrated (4,4)-nets in [Cu(4,4'-bpdz)(2)(H(2)O)(2)]S(2)O(6) were closely related to 4,4'-bipyridine compounds.

Silver(I) sulfate coordination polymers with 4,4'-bipyridazine and pyridazino[4,5-d]pyridazine.

Poly[[micro(4)-4,4'-bipyridazine-micro(5)-sulfato-disilver(I)] monohydrate], [[Ag(2)(SO(4))(C(8)H(6)N(4))].H(2)O](n), (I), and poly[[aqua-micro(4)-pyridazino[4,5-d]pyridazine-micro(3)-sulfato-disilver(I)] monohydrate], [[Ag(2)(SO(4))(C(6)H(4)N(4))(H(2)O)].H(2)O](n), (II), possess three- and two-dimensional polymeric structures, respectively, supported by N-tetradentate coordination of the organic ligands [Ag-N = 2.

Diaquabis[4-(4H-1,2,4-triazol-4-yl)benzoato-kappa2O,O']cobalt(II), and the cadmium(II) and copper(II) analogues: new self-complementary hydrogen-bond donor/acceptor modules for designing hydrogen-bonded frameworks.

In the isostructural title complexes, [M(C(9)H(6)N(3)O(2))(2)(H(2)O)(2)] [M = Co(II), (I), Cd(II), (II), and Cu(II), (III); the metal centres reside on a twofold axis in the space group C2/c for (I) and (II)], the metal centres are surrounded by four O atoms from two O,O'-bidentate carboxylate groups and by two trans-coordinated aqua ligands, forming a distorted octahedral environment. The molecules possess four hydrogen-bond donor (two aqua ligands) and four hydrogen-bond acceptor sites (two triazole groups), and aggregate by self-association, forming two-dimensional hydrogen-bonded frameworks [via O-H..

Synthesis of new organic super acids-N-(trifluoromethylsulfonyl)imino derivatives of trifluoromethanesulfonic acid and bis(trifluoromethylsulfonyl)imide.

Salts of N-trifluoromethylsulfonyl derivatives of trifluoromethyl- and phenylsulfonimidoyl imides have been synthesized by two different routes. Both methods are one-pot reactions, that run in mild conditions with good yields. Two novel organic super acids: bis[N-(trifluoromethylsulfonyl)trifluoromethanesulfonimidoyl]imide and N,N'-bis(trifluoromethyl-sulfonyl)diimino trifluoromethanesulfonic acid were prepared and the structure of their potassium salts was obtained by single-crystal X-ray diffraction.

Extended coordination frameworks incorporating heterobimetallic squares.

The molecular structure of aluminium and iron(III) complexes with 3-phenyl and 3-(4-pyridyl) (HL) substituted acetylacetonate ligands is appreciably distorted. For AlL3 and FeL3 this shows that the orientation of the side pyridyl-N donor atoms lone pairs is about 90 and 135 degrees which favours the assembly of heterobimetallic square patterns in Al(Fe)L3 complexes with metal ions. This was employed for the modular construction of semi-regular heterobimetallic networks, in which the pyridyldiketonate ligands bridge pairs of Fe(Al)/Cd(Co) metal ions and support the structure of 1D and 2D coordination polymers.

Self-assembly sodalite-like framework.

The dense packing of shape complementary N-donor molecules dominates the self-assembly of coordination polymers possessing sodalite-like topology and supports nanosize molecular cages.

Synthesis of a new polyfluorinated vinylogue of tetrathiafulvalene through 1,3-dipolar cycloaddition of ethyl beta-bromoperfluorodithiocrotonate with dimethyl acetylenedicarboxylate.

The ethyl ester of beta-bromoperfluorodithiocrotonic acid reacts with dimethyl acetylenedicarboxylate to give 1,4-difluoro-2,3-bis(trifluoromethyl)-but-2-ene-1,4-diylidene-2,2'-bis(4',5'-dicarbomethoxy-1',3'-dithiole) (4), a new type of vinylogue of tetrathiafulvalene. The thermal transformations of this compound lead, depending on the temperature, to the formation of the cyclization products: 11,14-difluoro-2,3,8,9-tetra(carbomethoxy)-12,13-bis(trifluoromethyl)-1,4,7,10-tetrathiadispiro[4.0.

Mixed-anion complexes with a bipyrazolyl ligand. A new entry to a realm of three-dimensional five-connected coordination topologies.

Cross-linking of corrugated square grid coordination layers by anionic bridging groups generates five-connected coordination networks; the 3D topologies of mixed-anion cobalt(II) and nickel(II) complexes with a tetramethyl-substituted 4,4'-bipyrazolyl ligand are supported by mu-SO4(2-) functions and exist as neutral or cationic five-connected arrays involving additional terminal (NCS-) or non-coordinated (NO3-, ClO4-) groups.