Dodecanuclear Copper Research Articles

A dodecanuclear copper(ii) cage self-assembled from six dicopper building units

Reaction of the dinucleating phenol-based ligand, H3bpmp (2,6-bis-[(3-hydroxy-propylimino)-methyl]-4-methyl-phenol), with Cu(2+) ions in the presence of a hybrid base (NEt3 and NaN3) necessary for the in situ generation of required numbers of hydroxido ions, results in the formation of a novel NO3(-) capped and HO(-) supported {Cu12} coordination complex {Cu6(μ3-OH)3(μ3-Hbpmp)3(μ3-NO3)}2(NO3)2(OH)2·2H2O·2MeOH (1). When the components are combined in right proportions (metal : ligand : NEt3 : NaN3 = 2 : 1 : 3 : 2) in MeOH, twelve Cu(2+) ions assemble in a cuboctahedral geometry, containing six square and eight triangular faces around a considerable void space. Six of the eight [Cu3] triangular faces are bound by the six Hbpmp(2-) ligands with six free pendant propanol arms around the central hexagonal plane. X-ray structure determination indicates new geometrical features for the core formation and reveals the face-capping potential of the H3bpmp ligand for the growth of a cuboctahedral coordination cage with the support of anions like HO(-) and NO3(-). The experimentally observed (J/kB = -173 K) strong antiferromagnetic coupling within the Cu12 complex has been justified by the DFT calculations.

Syntheses, structures and photoluminescent properties of three d10 coordination architectures based on in-situ 1,3,5-triazine derivatives

In the presence of aromatic carboxylic acids, three new d10 transition metal coordination polymers, [Ag(PAHT)]n(1), [Ag2(HCA)]n(2) and [Cu6(CA)2(H2O)]n(3) (HPAHT=2-phenyl-4-amino-6-hydroxy-1,3,5-triazine, H3CA=cyanuric acid) have been synthesized based on in-situ 1,3,5-triazine derivatives resulting from 2,4-diamino-6-phenyl-1,3,5-triazine, 2-chloro-4,6-diamino-1,3,5-triazine and melamine under hydrothermal conditions. Complexes 1–3 have been characterized by single-crystal X-ray diffraction, IR spectra, elemental analysis and thermogravimetric analysis (TGA). The compound 1 exhibits a uninodal three-connected 3D network with a rare lig LiGe type topology, which contains right-handed and left-handed [Ag(PAHT)]n helical chains. For compound 2, the 3D network is comprised of 2D sheet by strongly Ag–O and weakly Ag(I)…Ag(I) interactions. In compound 3, it is infrequently observed that dodecanuclear copper(I) units as secondary building units (SBUs) construct 3D network by the ligands CA3− with a rare uninodal 10-connected bct topology (312.428.55). The photoluminescent properties of three compounds have also been measured.

Two new metal–organic frameworks based on cyclic dodecanuclear copper units

Two new metal–organic frameworks based on cyclic-type dodecanuclear copper units, (Me4N)6[Cu12(OMe)6(pz)6(BTC)6]·18H2O 1 and (Me4N)6[Cu12(OH)6(pz)6(BTC)6]·21H2O 2 (pz = pyrazolate, BTC = 1,3,5-benzenetricarboxylate), have been prepared by the solvothermal reactions of copper salts, Hpz and H3BTC ligands. The cyclic-type Cu12 unit in 1 and 2 is constructed by twelve CuII ions linked together by μ2-OH or μ2-OMe and unidentate carboxylate groups at the inner- and μ-pz and bidentate carboxylate groups at the outer surface of the toroid. In 1 and 2, each Cu12 unit is connected to 12 other units by BTC linkers, leading to 12-connected three-dimensional porous frameworks. The photocatalytic investigations indicate that compounds 1 and 2 exhibit photocatalytic activity for the degradation of RhB.

A 12-connected metal–organic framework constructed from an unprecedented cyclic dodecanuclear copper cluster

A 12-connected metal-organic framework based on an unprecedented cyclic Cu(12) cluster with a large internal cavity has been prepared, and its cation exchange property was determined.

A Dodecanuclear Copper(I) Complex Containing a Cubic (CuS)4 Core Stabilized by a Tripodal (N,N,P)-Chelating Ligand

We present the structure elucidation of a copper(I) complex of a monoanionic phosphanylalkyl-diimido sulfonate ligand centered by a sulfur-copper cube. It has the formula [{Me2PCH2S(NSiMe3)2}4 Cu8{CuS}4] (2) and is the first example of a copper(I) complex of this new ligand type.

A Dodecanuclear Copper(I) Complex Containing a Cubic (CuS)4 Core Stabilized by a Tripodal (N,N,P)-Chelating Ligand

A Dodecanuclear Copper(I) Complex Containing a Cubic (CuS)4 Core Stabilized by a Tripodal (N,N,P)-Chelating Ligand

A 12-Connected Dodecanuclear Copper Cluster with Yellow Luminescence

The 3-D 12-connected metal-organic framework [Cu(12)Br(2)(CN)(6/2)(SCH(3))(6)][Cu(SCH(3))(2)], containing dodecanuclear copper clusters, has been solvothermally synthesized and exhibits efficient yellow luminescence. The emission mechanism was studied in detail to elucidate the relationship of the luminescent properties and crystal structures, which is helpful for the design and synthesis of more efficient luminescent materials.

Self-Assembly of a Chiral Carbonate- and Cytidine-Containing Dodecanuclear Copper(II) Complex: a Multiarm-Supplied Globular Capsule

A dodecanuclear copper(II) globular-shaped structure has been obtained with the cytidine nucleoside and the templating carbonate anion. It shows receptor properties through anion-cation and multiple anion-pi interactions toward ClO 4 (-) as well as an overall antiferromagnetic coupling.

Barrel- and Crown-Shaped Dodecanuclear Copper(II) Cages Built from Phosphonate, Pyrazole, and Hydroxide Ligands

The reaction of Cu(ClO4)2. 6H2O with t-BuP(O)(OH)2 and 3,5-(CF3)2PzH in the presence of triethylamine afforded the dodecanuclear cage ([Et3NH]2[Cu12(mu-3,5-(CF3)2Pz)6(mu3-OH)6(mu-OH)3(mu3-t-BuPO3)2(mu6-t-BuPO3)3][t-BuPO2OH][C6H5CH3]2) (2). The molecular structure of this cage revealed that it possesses a barrel-shaped architechture. The cage structure is built by the cumulative coordination action of phosphonate, hydroxide, and pyrazolyl ligands. A similar reaction involving Cu(NO3)2. 3H2O, t-BuP(O)(OH)2, 3,5-dimethylpyrazole, and triethylamine afforded another dodecanuclear cage [Cu12(mu-DMPz)8(eta1-DMPzH)2(mu4-O)2(mu3-OH)4(mu3- t-BuPO3)4].3MeOH (3). The latter is crown-shaped and is built by the coordination of pyrazole, pyrazolyl, phosphonate, hydroxide, oxide, and methanol ligands. Both of the dodecanuclear cages are efficient nucleases in the presence of magnesium monoperoxyphthalate.

Transformation of Inorganic Sulfur into Organic Sulfur: A Novel Photoluminescent 3-D Polymeric Complex Involving Ligands in Situ Formation

The reaction of CuSCN with acetonitrile and methanol under solvothermal conditions yielded a novel 3-D polymeric photoluminescent complex containing dodecanuclear copper(I) clusters with methyl mercaptide. The synthesis involves in situ generation of ligands, which provides a model reaction to simulate the transformation of inorganic sulfur into organic sulfur under geothermic conditions.

Structure and Magnetism of a New Dodecanuclear CuII Complex with Acetato and Imidazolato Bridges, Formed by Oxidation of the Chelating Ligand 1,1,7,7‐Tetrakis(imidazol‐2‐yl)‐2,6‐diazaheptane

AbstractA novel dodecanuclear copper(II) complex [Cu12(tidhd)4(MeOH)8(CH3COO)8](MeOH)0.8 (Htidhd = 1,1,7,7‐tetrakis(imidazol‐2‐yl)‐2,6‐diaza‐1,6‐heptadiene) with imidazolato and acetato bridging ligands was synthesized by reaction of polyimidazole 1,1,7,7‐tetrakis(imidazol‐2‐yl)‐2,6‐diazaheptane (Htidahp) with copper acetate in a methanol solution. The complex crystallized in the triclinic space group P$\bar 1$ with a = 9.1204(1), b = 13.5139(2), c = 27.6925(5), α = 76.8006(6)°, β = 82.8066(7)°, γ = 76.4594(9)°, Z = 1. Structure analysis shows that the unit cell of the complex contains twelve copper(II) ions in three different coordination environments. The complex is centrosymmetric and the two hexanuclear units are linked by two μ3‐acetate anions [the Cu1−Cu1a distance is 3.5507(7) Å]. The magnetic superexchange interaction via the bridging imidazolate ligand appears to be the most important magnetic interaction in this complex. Magnetic susceptibility measurement vs. temperature in the range of 6−300 K were fitted to the parameters g = 2.05, Ja = −32.0 cm−1 and Jb = −5.45 cm−1. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)

Encapsulation of paramagnetic 3d1-vanadium(IV) in an antiferromagnetically coupled dodecanuclear copper(II) cage.

A mixed metal cluster [Cu12VO5L6] of a pentadentate Schiff base (H3L) containing vanadium(IV) in a dodecanuclear copper(I) cage is prepared by vanadyl templated self assembly of dicopper(II) precursor and the structurally characterized complex shows antiferromagnetic coupling involving copper(II) centers, which leads close to diamagnetism for the Cu(II) cage below 40 K in the presence of an encapsulated paramagnetic 3d1-V(IV) atom.

Cu12 (P2 Se6 ){Se2 P(OR)2 }8 ]: Discrete Copper Clusters Containing an Ethane-Like Hexaselenodiphosphate(IV).

The coexistence of P4+ and P5+ in one complex and the presence of an ethane-like hexaselenodiphosphato ligand, P2 Se64- , are the novel features of the title compounds (see structure, in which R=Et or iPr; OR groups omitted for clarity). The coordination mode of P2 Se64- in these dodecanuclear copper species is unprecedented and has not even been identified in any mixed ligands containing Group 15/16 elements.

A Dodecanuclear Copper(II) Cage Containing Phosphonate and Pyrazole Ligands This work was supported by a grant from the Department of Science and Technology (DST), New Delhi (V.C.). V.C. is also grateful to the Homi Bhabha Fellowship Council for a fellowship. We thank the DST for funding the National Facility for X-ray Crystallography at the Indian Institute of Technology, Kanpur. We

Two symmetry-related hexameric units that are linked to each other form the basis of the structure of a novel dodecanuclear copper cluster (one hexameric unit is shown). The cluster is assembled in a one-pot synthesis from copper(II) chloride, tert-butylphosphonic acid, 3,5-dimethylpyrazole, and triethylamine. The core of the cluster is encased in a lipophilic sheath.

A novel antiferromagnetically coupled, dimeric, dodecanuclear copper(II) complex involving two macrocyclic ligands each with a ‘benzene-like’ arrangement of six copper centres

Template condensation of 2,6-diformyl-4-methylphenol with 1,3-diamino-2-hydroxypropane, in the presence of copper(II) nitrate and a base, results in the formation of a novel dimeric, dodecacopper(II) complex of a 30-membered macrocyclic ligand (H6M), with a pseudo-hexagonal, ‘benzene-like’ arrangement of metal centres and an alternating double (µ2-OPh, µ2-OH) and single (µ2-OR) bridge arrangement within each ring.