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Outer-shell s 0 /p 0 orbital mixing with d 10 orbitals and symmetry reduction upon cupriphication of cyclic trinuclear trigonal-planar gold(I) complexes are found to sensitize ground-state Cu(I)-Au(I) covalent bonds and near-unity phosphorescence quantum yields. Heterobimetallic Au 4 Cu 2 {[Au 4 (μ-C 2 ,N 3 -EtIm) 4 Cu 2 (μ-3,5-(CF 3 ) 2 Pz) 2 ], (4a)}, Au 2 Cu {[Au 2 (μ-C 2 ,N 3 -BzIm) 2 Cu(μ-3,5-(CF 3 ) 2 Pz)], (1) and [Au 2 (μ-C 2 , N 3 -MeIm) 2 Cu(μ-3,5-(CF 3 ) 2 Pz)], (3a)}, AuCu 2 {[Au(μ-C 2 ,N 3 -MeIm)Cu 2 (μ-3,5-(CF 3 ) 2 Pz) 2 ], (3b) and [Au(μ-C 2 ,N 3 -EtIm)Cu 2 (μ-3,5-(CF 3 ) 2 Pz) 2 ], (4b)} and stacked Au 3 /Cu 3 {[Au(μ-C 2 ,N 3 -BzIm)] 3 [Cu(μ-3,5-(CF 3 ) 2 Pz)] 3 , (2)} form upon reacting Au 3 {[Au(μ-C 2 ,N 3 -(N-R)Im)] 3 ((N-R)Im = imidazolate; R = benzyl/methyl/ethyl = BzIm/MeIm/EtIm)} with Cu 3 {[Cu(μ-3,5-(CF 3 ) 2 Pz)] 3 (3,5-(CF 3 ) 2 Pz = 3,5-bis(trifluoromethyl)pyrazolate)}. The crystal structures of 1 and 3a reveal stair-step infinite chains whereby adjacent dimer-of-trimer units are noncovalently packed via two Au(I)⋯Cu(I) metallophilic interactions, whereas 4a exhibits a hexanuclear cluster structure wherein two monomer-of-trimer units are linked by a genuine d 10 -d 10 polar-covalent bond with ligandunassisted Cu(I)-Au(I) distances of 2.8750(8) Å each-the shortest such an intermolecular distance ever reported between any two d 10 centers so as to deem it a "metal-metal bond" vis-à-vis "metallophilic interaction." Density-functional calculations estimate 35-43 kcal/mol binding energy, akin to typical M-M single-bond energies. Congruently, FTIR spectra of 4a show multiple far-IR bands within 65-200 cm −1 , assignable to v Cu-Au as validated by both the Harvey-Gray method of crystallographic-distance-to-force-constant correlation and dispersive density functional theory computations. Notably, the heterobimetallic complexes herein exhibit photophysical properties that are favorable to those for their homometallic congeners, due to threefold-to-twofold symmetry reduction, resulting in cuprophilic sensitization in extinction coefficient and solid-state photoluminescence quantum yields approaching unity (Φ PL = 0.90-0.97 vs. 0-0.83 for Au 3 and Cu 3 precursors), which bodes well for potential future utilization in inorganic and/or organic LED applications. Here, we show that outer 4s/p (Cu I ) and 6s/p (Au I ) orbitals can admix with the respective valence 3d and 5d orbitals to sensitize a bona fide polar-covalent metal-metal bond between two d 10 centers manifest by two rather short, 2.8750(8) Å, Cu(I)-Au(I) bonds without any ligand-bite-size assistance. The reduced symmetry in this family of complexes is also shown to impart higher extinction coefficients and phosphorescence quantum yields than those attained by the parent homometallic precursor complexes.Heterometallic complexes are remarkable molecules owing to their unique catalytic and optoelectronic properties (2, 3). Heterometallic species involving coinage metals have received immense attention owing to their fascinating structural a...

Following an increasing interest in the gold drug therapy field, nine new neutral azolate gold(I) phosphane compounds have been synthesized and tested as anticancer agents. The azolate ligands used in this study are pyrazolates and imidazolates substituted with deactivating groups such as trifluoromethyl, nitro or chloride moieties, whereas the phosphane co-ligand is the triphenylphosphane or the more hydrophilic TPA (TPA = 1,3,5-triazaphosphaadamantane). The studied gold(I) complexes are: (3,5-bis-trifluoromethyl-1H-pyrazolate-1-yl)-triphenylphosphane-gold(I) (1), (3,5-dinitro-1H-pyrazolate-1-yl)-triphenylphosphane-gold(I) (2), (4-nitro-1H-pyrazolate-1-yl)-triphenylphosphane-gold(I) (5), (4,5-dichloro-1H-imidazolate-1-yl)-triphenylphosphane-gold(I) (7), with the related TPA complexes (3), (4), (6) and (8) and (1-benzyl-4,5-di-chloro-2H-imidazolate-2-yl)-triphenylphosphane-gold(I) (9). The presence of deactivating groups on the azole rings improves the solubility of these complexes in polar media. Compounds 1-8 contain the N-Au-P environment, whilst compound 9 is the only one to contain a C-Au-P environment. Crystal structures for compounds 1 and 2 have been obtained and discussed. Interestingly, the newly synthesized gold(I) compounds were found to possess a pronounced cytotoxic activity on several human cancer cells, some of which were endowed with cis-platin or multidrug resistance. In particular, among azolate gold(I) complexes, 1 and 2 proved to be the most promising derivatives eliciting an antiproliferative effect up to 70 times higher than cis-platin. Mechanistic experiments indicated that the inhibition of thioredoxin reductase (TrxR) might be involved in the pharmacodynamic behavior of these gold species.

A comparative study on the tendency of a new trinuclear silver(I) pyrazolate, namely, [N,N-(3,5-dinitropyrazolate)Ag]3 (1), and a similar compound known previously, [N,N-[3,5-bis(trifluoromethyl)pyrazolate]Ag]3 (2), to adsorb small volatile molecules was performed. It was found that 1 has a remarkable tendency to form adducts, at room temperature and atmospheric pressure, with acetone, acetylacetone, ammonia, pyridine, acetonitrile, triethylamine, dimethyl sulfide, and tetrahydrothiophene, while carbon monoxide, tetrahydrofuran, alcohols, and diethyl ether were not adsorbed. On the contrary, 2 did not undergo adsorption of any of the aforementioned volatile molecules. Adducts of 1 were characterized by elemental analysis, IR, thermogravimetric analysis (TGA), Brunauer-Emmett-Teller (BET) surface area, and diffusion NMR measurements. The crystal structures of 1·2CH3CN and compound 3, derived from an attempt to crystallize the adduct of 1 with ammonia, were determined by single-crystal X-ray diffractometric studies. The former shows a sandwich structure with a 1:2 stoichiometric [Ag3]/[CH3CN] ratio in which one acetonitrile molecule points above and the other below the centroid of the Ag3N6 metallocycle. Compound 3 formed via rearrangement of the ammonia adduct to yield an anionic trinuclear silver(I) derivative with an additional bridging 3,5-dinitropyrazolate and having [Ag(NH3)2](+) as the counterion, [Ag(NH3)2][N,N-(3,5-dinitropyrazolate)4Ag3]. Irreversible sorption and/or decomposition upon vapor exposure are desirable advantages toward toxic gas filtration applications, including ammonia inhalation. TGA confirms the analytical data for all of the samples, showing weight loss for each adsorbed molecule at temperatures significantly higher than the corresponding boiling temperature, which suggests a chemical-bonding nature for adsorption as opposed to physisorption. BET surface measurements of the "naked" compound 1 excluded physical adsorption in its porous cavities. Density functional theory simulation results are also consistent with the chemisorption model, explain the experimental adsorption selectivity for 1, and attribute the lack of similar adsorption by 2 to significantly less polarizable electrostatic potential and also to strong argentophilic bonding whose energy is even higher than the quadrupole-dipole adduct bond energy upon proper selection of the density functional.

Two scorpionates sodium trihydro(3-nitro-pyrazol-1-yl)borate (Na[H(3)B(3-(NO(2))pz)]) and sodium hydrotris(3-nitro-pyrazol-1-yl)borate (Na[HB(3-(NO(2))pz)(3)]), featuring electron withdrawing substituents, have been synthesized in high yield starting from 3(5)-nitropyrazole and sodium borohydride. The treatment of CuX (X = (CH(3)CN)(4)PF(6), Cl or I) with Na[H(3)B(3-(NO(2))pz)], Na[HB(3-(NO(2))pz)(3)] or the related bis(pyrazolyl)borate Na[H(2)B(3-(NO(2))pz)(2)] in the presence of triphenylphosphine or tert-butyl isocyanide afforded the corresponding (azolyl)borate supported copper(I) triphenylphosphine or tert-butyl isocyanide adducts. These compounds have been characterized by elemental analyses, FT-IR, ESI-MS and multinuclear NMR spectroscopy. X-Ray crystal structures of [H(3)B(3-(NO(2))pz)]Cu[P(C(6)H(5))(3)](2), [H(2)B(3-(NO(2))pz)]Cu(CNt-Bu)(2), and [HB(3-(NO(2))pz)(3)]Cu[P(C(6)H(5))(3)], as well as that of the {[HB(3-(NO(2))pz)(3)]Na}(4) are also reported. The latter displays a particularly interesting tetrameric structure with each tris(pyrazolyl)borate adopting an unusual inverted configuration and serves as a bridging ligand for three different sodium ions.