White light: [{Au(L)}3] (L=3-(2-thienyl)pyrazolate) gives dual emission, one from an organic chromophore the other aurophilic stacking interactions. The resulting blue–green and orange–red emissions can be tuned to approach white-light by modulating aggregation behavior of cluster.

We observed an unusual reversible aggregation process showing stimuli-responsive structural dynamics and optical changes attributed to the formation of a sandwich-like Au3-Ag-Au3 cluster, which can be synthesized through both solution mechanochemical methods. Unlike many other heteronuclear gold-silver clusters, affinity two cyclic Au3 complexes Ag(I) ion is solely bound by ligand unsupported Au-Ag bonding. The assembly/disassembly behavior, further forming nanoaggregates, controllable...

Abstract Two classical copper(I)‐cluster‐based luminophores, namely, Cu 4 I and [Cu 3 Pz ] 2 (Pz=pyrazolate), are immobilized in a supramolecular system through the formation of metal–organic framework (MOF) materials. This series luminescent MOF materials, (NH )Cu ( L1 ) n , CH L2 =3‐(4‐pyridyl)‐5‐( p ‐tolyl)pyrazolate; =3‐(4‐pyridyl)‐5‐(2,4‐dimethylphenyl)pyrazolate), exhibit diverse thermochromism attributed to relative functioning efficacy two coordination luminophores. Such an...

Artificial molecular architecture from a large number of subcomponents (>50) via self-assembly remains formidable challenge for chemists. Reaction 38 components [14 Ni(2+) and 24 N-methyl-1-(4-imidazolyl)methanimine] under solvothermal conditions reproducibly leads to the formation high-symmetry coordination cage. This polyhedral cage can also be obtained in high yield by 62 commercially available (24 methylamine, 4-formylimidazole, 14 Ni(2+)) mild involving synchronized both dynamic...

Luminescence mechanochromism of the well-known Cu3Pz3-type (Pz = pyrazolate) complexes is reported here, which unusual for this family. Two types new Cu3Pz3 complexes, namely Cu3(EBPz)3 (1; EBPz ethyl-4'-benzoate-3,5-dimethylpyrazolate) and Cu3(MBPz)3 (polymorphs 2a-c; MBPz methyl-4'-benzoate-3,5-dimethylpyrazolate), have been synthesized characterized. Their crystal structures exhibit a similar chairlike dimer stacking supported by short Cu···Cu contacts, would facilitate formation...

One molecule, two response mechanisms: a pair of newly-designed cyclic trinuclear Cu(<sc>i</sc>) complex crystalline polymorphs are engineered, which show excellent luminescent piezochromism and pressure-induced phosphorescence enhancement, respectively.

A supramolecular dual emissive system incorporating two classical copper(I)-cluster-based luminophores, namely, Cu4I4 and Cu3Pz3 (Pz = pyrazolate), is reported. The targeted luminescent coordination polymer exhibits reversible thermochromism spanning from green to orange-red.

A polycatenated HOF has been constructed from supramolecular embraced pairs of macrocyclic modules, featuring fluorescent detection nitrobenzene in water.

All wrapped up: Supramolecular polymeric helices were fabricated by using cluster helicates as templates. The helicity of the template (see picture; gold spheres: Ni or Zn; blue O), upon hydrothermal treatment with CuSCN (gray spheres), is transferred to strands resulting copper-based coordination polymer, which around helicate units in final product. Supporting information for this article available on WWW under http://www.wiley-vch.de/contents/jc_2002/2008/z704874_s.pdf from author. Please...

Reactions of CuX (X = Br(-), I(-) or CN(-)) with various types 2,2'-dipyridylamine (dpa) derivatives have been performed via a hydrothermal-solvothermal method and the products structurally characterized by X-ray crystallography. Four ligands different coordination motifs were employed in reactions, including angular N,N,N',N'-tetra(2-pyridyl)-2,6-pyridinediamine (tppda); linear N,N,N',N'-tetra(2-pyridyl)-1,4-phenylenediamine (tppa) N,N,N',N'-tetra(2-pyridyl)biphenyl-4,4'-diamine (tpbpa);...

Two unprecedented 3D polyknotted isomers, arisen from different linkage modes of SCN-, were obtained 3,5-bis(4-pyridyl)-1H-pyrazole (Hbppz) and CuSCN under conditions.

A chiral heterometallic complex, obtained from the solvothermal reaction of [Zn(4-pytpy)2](BF4)2 [4-pytpy=4'-(4-pyridyl)-2,2':6',2''-terpyridine] and CuCN, exhibits a rare self-catenated network formed by two 3D cationic one anionic frameworks.

By systematically varying the geometric length and electronic properties of second ligating ligands halogen (Cl(-), Br(-), I(-)) pseudohalogen (CN(-), SCN(-), N(3)(-)) anions, we synthesized 11 isomeric/isostructural copper(I) complexes: [Cu(2)(L3-3)I](n) (1), [Cu(2)(L4-4)Br](n) (2-Br), [Cu(2)(L4-4)Cl](n) (2-Cl), [Cu(2)(L3-4)(CN)](n) (3), [Cu(2)(L3-3)(CN)](n) (4), [Cu(3)(L4-4)(CN)(2)](n) (5), {[Cu(2)(L4-4)Br](2)·CuBr}(n) (6-Br), {[Cu(2)(L4-4)Cl](2)·CuCl}(n) (6-Cl), [Cu(2)(L4-4)(SCN)](n)...

Six daughter complexes based on two-dimensional (2-D) luminescent Cu4I4-Cu3Pz3 (Pz = pyrazolate) coordination networks, which exhibit an uncommon Cu4I4L3L' (L pyridine; L' acetonitrile, pyridine, pyrazine, 1,4-diazabicyclo[2.2.2]octane, triphenylphosphine, none) local configuration, were prepared through a postsynthetic modification method starting from parent complex (L' NH3). This work has successfully implemented the single-site substitution of Cu4I4-based frameworks, have rarely been...

The Cu2(azole)2-SBU (secondary building unit) versatility is illustrated in the construction of cyano-bridged copper(I)-tetrazole coordination frameworks through situsolvo(hydro)thermal syntheses, yielding {[Cu2(μ3-Mtta)2(CN)][Na(CH3CN)]}n (1), with a common non-interpenetrated 3D pcu net, and {[Cu4(μ3-HMtta)2(CN)3](OH)}n (2), an unprecedented four-fold interpenetrated lim net.

This work focuses on the investigation of targeting homometallic mixed-valence copper(I/II) Schiff base coordination polymers (CPs) via a proposed synthetic strategy, namely, in situ immobilization metalloligands. We have designed and synthesized three structurally related isomeric ligands, all which contain chelating bridging sites and, accordingly, obtained two distinctly shaped metalloligands, [Cu(L1)2] (1) [Cu(L3)2] (3a) [HL = pyridinecarbaldehyde isonicotinoyl hydrazone]. By introducing...

Exohedral cuprofullerenes with 6-, 12-, or 24-nuclearity were obtained by utilizing fluorocarboxylic/dicarboxylic acid under solvothermal conditions. The 24-nuclear molecule presents a C60@Cu24 core–shell structure rhombicuboctahedron Cu24 coated on the C60 core, representing highest nuclearity in metallofullerene. resultant complexes show an efficient absorption of visible light as opposed to pristine C60. TD-DFT calculations revealed charge transfer from Cu(I) and O atoms fullerene moiety...

The crystal packing and photoluminescent properties of coordination cage can be fine-tuned <italic>via</italic> the encapsulation aromatic guests with different substituents.

Solvothermal reactions of CuSCN, metal (Mn2+, Fe2+, Co2+, Ni2+, Cu2+) sulfate, and terpyridine (2,2':6',2' '-terpyridine or 4'-p-tolyl-2,2':6',2' '-terpyridine) in the presence triphenylphosphine yielded a series hybrid coordination compounds, which situ formed bis(terpyridine) complex cations are encapsulated by 3D anionic network entangled 2D heartlike networks, forming encapsulation polypseudorotaxane supramolecules. The play role as template to direct fabrication structures.

Solvothermal reactions of CuII salts and 3,5-bis(4-pyridyl)pyrazole (HL) under various conditions gave three different types crystalline compound, namely [Cu2(Cu5L6)]BF(4).5 H2O (1 a), [Cu2(Cu5L6)]ClO(4).5 b), [Cu7(CN)2(Cu5L6)2][BF4]3 (2). 1 a b were obtained in ethanol NH3.H2O, whereas 2 was methanol NH3.H2O. The complexes constructed by incorporating new pentanuclear copper(I) pyrazolate bis(triple helical) cluster helicates (Cu5L6) as the second building units (SBUs), which many twelve...

A highly luminescent supramolecular Cu₂I₂(NH₃)₂-sandwiched Cu₃(pyrazolate)₃ π-acid⋯base adduct, stabilized by intermolecular Cu₃⋯I (π-acid⋯base), Cu⋯Cu and N⋯H interactions, is reported as a temperature sensor in wide range.

Three Cu3Pz3-based isostructural complexes (Cu3L3)2(CuX)2 (labeled as 1-ClO4, 1-NO3, and 1-Br, where X = ClO4-, NO3-, Br-, respectively) were prepared by solvothermal reactions of an angular bifunctional pyridyl-pyrazole ligand, 4-(pyridin-4'-ylthio)-3,5-dimethyl-1 H-pyrazole ( HL), with Cu(ClO4)2, Cu(NO3)2, CuBr, respectively. Pyrazolate (Pz) groups are highly specific to form planar trinuclear Cu3Pz3 units. Two Cu3L3 units further connected two CuX through NPy-Cu-NPy (Py 4-pyridyl) bonds...

Reported herein are a pair of supramolecular pseudo-isomers, namely, (Cu3I3)(Cu3L3)2·H2O (1) and (Cu3I3)(Cu3L3)2 (2) (L = 3-(4-pyridyl)-5-isobutyl-pyrazolate), both which incorporate Cu3Pz3 (Pz pyrazolate) Cu3I3 clusters as luminophores. The two complexes show distinct yellow (570 nm) orange (638 emissions, ascribed to the formation excimer exciplex involving same or different copper(I)-cluster-based

Weißlicht: [{Au(L)}3] (L=3-(2-Thienyl)pyrazolat) zeigt eine duale Emission, zum einen von einem organischen Chromophor, anderen durch aurophile Stapelwechselwirkungen. Die resultierenden blau-grünen und orange-roten Emissionen können Modulation des Aggregationsverhaltens Clusters so reguliert werden, dass man weißes Licht erhält.