Two new bis-bidentate bridging ligands have been prepared, L (naph) and (anth), which contain two chelating pyrazolyl-pyridine units connected to an aromatic spacer (naphthalene-1,5-diyl anthracene-9,10-diyl respectively) via methylene connectors. Each of these reacts with transition metal dications having a preference for octahedral coordination geometry afford {M 8L 12} (16+) cages (for M = Cu, Zn; (naph), Co, Ni, Cd) approximately cubic arrangement ions ligand spanning each the twelve...

A tripodal cyclotriveratrylene-based ligand with chelating 2,2'-bipyridine arms self-assembles either Zn(NO3)2 or Co(NO3)2 to give 3-D trigonal bipyramidal [M3L2] cage assemblies. These cages triply interlock forming [2]catenane species that have been characterized by mass spectrometry and, in the case of Zn(II) complex, X-ray crystallography.

Two new types of coordination cage have been prepared and structurally characterized: [M16(mu-L1)24]X32 are based on a tetra-capped truncated tetrahedral core bridging ligand L1 along each the 24 edges; [M12(mu-L1)12(mu3-L2)4]X24 cuboctahedral which is supported by combination face-capping ligands L2 edge-bridging L1. The difference between two illustrates how combinations with different modes can generate cages not available using one type its own.

Star treatment: Host molecule tris(isonicotinoyl)cyclotriguaiacylene self-assembles with Pd(NO3)2 to form a [Pd6L8]12+ metallo-supramolecular cage of over 3 nm in diameter that resembles stella octangular structure (see picture). ESMS and DOSY NMR studies show the assembly also exists solution hydrodynamic radius approximately 19 Å.

The tetradentate ligand Lnaph contains two N-donor bidentate pyrazolyl−pyridine units connected to a 1,8-naphthyl core via methylene spacers; L*45 and L*56 are chiral ligands with structure similar that of but bearing pinene groups fused either C4 C5 or C6 the terminal pyridyl rings. complexes [Cu(Lnaph)](OTf) [Ag(Lnaph)](BF4) have unremarkable mononuclear structures, CuI being four-coordinate AgI two-coordinate additional weak interactions (i.e., "2 + 2" coordinate). In contrast,...

Reaction of a tris-bidentate ligand L1 (which can cap one triangular face metal polyhedron), bis-bidentate L2 span edge and range M2+ ions (M = Co, Cu, Cd), which all have preference for six coordination geometry, results in assembly the mixed-ligand polyhedral cages [M12(μ3-L1)4(μ-L2)12]24+. When components are combined correct proportions [M2+:L1:L2 3:1:3] MeNO2, this is sole product. The array 12 cations has cuboctahedral containing square eight faces around substantial central cavity;...

Crystalline M3L2 complexes with either single cage or triply interlocking [2]catenane chiral structures are formed the self-assembly of host-like ligands transition metals.

Reaction of the bis-bidentate bridging ligand L3, in which two bidentate chelating 3(2-pyridyl)pyrazole units are separated by a 3,3′-biphenyl spacer, with Co(II) salts affords tetranuclear cage complexes composition [Co4(L3)6]X8 (X = [BF4]−, [ClO4]−, [PF6]− or I−) four 6-coordinate ions an approximately tetrahedral array connected six ligands, one spanning each edges Co4 tetrahedron. In every case, X-ray crystallography reveals that 'apical' ion has fac tris-chelate geometry, whereas other...

A chiral bridging ligand affords a single diastereoisomer of tetrahedral M4L6 cage complex in which the optical rotation each is increased by factor 5 on coordination.

The coordination chemistry of a series di- and tri-nucleating ligands with Ag(I), Hg(I) Hg(II) has been investigated. Most the contain two or three N,N'-bidentate chelating pyrazolyl-pyridine units pendant from central aromatic spacer; one contains binding sites (2 + 3 2-dentate) in linear sequence. A thirteen complexes structurally characterised displaying wide range structural types. Bis-bidentate bridging react Ag(I) to give which is four-coordinate bidentate donors, but can take form...

An unprecedented 2.5 nm array of π interactions between eight aromatic rings drives the formation a [2]catenane. Disruption this through use longer ligands results in only single, uncatenated rings. The catenated complex is shown to persist solution alongside its constituent metallomacrocycles.

Reaction of the bis-bidentate ligand L1, having two bidentate pyrazolyl-pyridine termini, with Co(II) or Zn(II) results in formation complexes [M8(L1)12]X16 (X = perchlorate tetrafluoroborate); [Zn8(L1)2](ClO4)16 has been structurally characterised and is a cube metal ion at each corner, bridging along edge, an anion central cavity.

A set of three potentially bridging ligands containing two tridentate chelating N,N',O-donor (pyrazole-pyridine-amide) donors separated by an o, m, or p-phenylene spacer has been prepared and their coordination chemistry with lanthanide(III) ions investigated. Ligand L(1) (p-phenylene spacer) forms complexes a 2:3 M:L ratio according to the proportions used in reaction mixture; Ln(2)(L(1))(3) contain 9-coordinate Ln(III) centres all spanning both metal ions, have cylindrical (non-helical)...

A series of clathrate and metal complexes with cyclotriveratrylene-like molecular host ligands show a similar dimeric homomeric inclusion motif in which ligand arm one is the intra-cavity guest another vice versa. This "hand-shake" found trinuclear transition complex [Cu(3)Cl(6)(1)]CH(3)CN1.5 H(2)O 1 tris(4-[2,2',6',2''-terpyridyl]benzyl)cyclotriguaiacylene; self-included M(4)L(4) tetrahedral metallo-supramolecular assembly [Ag(4)(2)(4)] (BF(4))(4) 2...

Responsive lanthanide complexes demonstrate differentiated modulated luminescence output upon exposure to metal di-cations in aqueous solution.

Self-assembly of the ligand L1 with Co2+ into a dinuclear triple helicate [Co2(L1)3]4+ produces an anion binding pocket which encapsulates perchlorate anions. Furthermore we demonstrate how this ability to bind anions can control self-recognition properties.

The syntheses of two chromophore-appended dipicolylamine-derived ligands and their reactivity with pentacarbonylchlororhenium have been studied. resultant complexes each possess the fac-Re(CO)3 core. L111-[bis(pyridine-2-ylmethyl)amino]methylpyrene L22 2-[bis(pyridine-2-ylmethyl)amino]methylquinoxaline were isolated via a one-pot reductive amination in moderate yield. corresponding rhenium good yields characterised by 1H NMR, MS, IR UV-Vis studies. X-Ray crystallographic data obtained for...

The synthesis of five new cyclotriveratrylene derivatives with 4-pyridyl side arms is reported, along the crystal structures three these. Three ligands extended 4-pyridylphenyl and a ligand derived from cyclotriphenolene have been shown to form [Pd6L8]12+ stella octangula assemblies using diffusion-ordered spectroscopy NMR electrospray MS techniques. This confirms generality octagula assembly, providing that show degree rigidity. more flexible ether-linked...

Pyridyl functionalized host molecules are oxidized to their N-oxide analogues and form a series of coordination polymers discrete complexes with transition metal cations. Complex {[Ag(3)(NMP)(6)(L1)(2)]·3(ClO(4))}(∞) where L1 = tris(isonicotinoyl-N-oxide)cyclotriguaiacylene, NMP N-methylpyrrolidone, is three-dimensional (3-D) 3,6-connected polymer pyrite-like (pyr) topology features ligand unsupported argentophilic interactions, while two-dimensional (2-D) the rarely reported kagome dual...

Everybody form a circle: Careful design of ligand strands and their reaction with Cu2+ ions leads to the formation title helicates. Incorporation differing numbers N-donor units within strand containing phenyl spacer results in pentanuclear head-to-tail circular helicate, whereas two different ligands heteroleptic helicate (see picture; green: Cu, red blue: ligands). Detailed facts importance specialist readers are published as "Supporting Information". Such documents peer-reviewed, but not...

Tris-allyl-cyclotriguaiacylene combines with silver salts to give a range of crystalline network structures and one discrete complex. A number different coordination modes are found within the complexes including η(2)-allyl, aryl, OR groups binding Ag(I). AgSbF(6) gives two types three-dimensional (3-D) polymer unusual topologies, along Ag(2)L(2) capsule dependent on reaction stoichiometry conditions. Isostructural chain AgBF(4) AgClO(4), while use Ag(CF(3)SO(3)) two-dimensional (2-D) 3-D...

We describe a ligand system that forms either dinuclear double helicate or mesocate dependent upon the size of metal ion steric bulk strand.

The amide-substituted unsymmetrical ligand L(1) upon coordination to Co(2+) forms the dinuclear triple helicate [Co(2)(L(1))(3)](4+) which exists as both possible C(1) and C(3) symmetric geometric isomers in solution, however, addition of nitrate ions, formation an anion binding cavity is favoured hence sole product isomer all three amide substituents are hydrogen bonded anion.