Miguel Monge

Combining Aurophilic Interactions and Halogen Bonding To Control the Luminescence from Bimetallic Gold−Silver Clusters

The luminescence in a series of new bimetallic gold-silver vapochromic structures can be efficiently switched among different colors simply by exposure to solvent vapors. The emission color in these systems is controlled by both aurophilic interactions and halogen bonding, which affect the emission energy through different orbitals.

Vapochromic behavior of {Ag2(Et2O)2[Au(C6F5)2]2}n with volatile organic compounds.

The vapochromic behaviors of {Ag2L2[Au(C6F5)2]2}n (L = Et2O (1), Me2CO (2), THF (3), CH3CN (4)) were studied. {Ag2L2[Au(C6F5)2]2}n (L = Et2O (1)) was synthesized by the reaction of [Bu4N][Au(C6F5)2] with AgOClO3 in 1:1 molar ratio in CH2Cl2/Et2O (1:2). 1 was used as starting material with THF to form {Ag2L2[Au(C6F5)2]2}n (L = THF (3)). 3 crystallizes in the monoclinic space group C2/c and consists of tetranuclear units linked together via aurophilic contacts resulting in the formation of a 1D polymer that runs parallel to the crystallographic z axis. The gold(I) atoms are linearly coordinated to two pentafluorophenyl groups and display additional Au...Ag close contacts within the tetranuclear units with distances of 2.7582(3) and 2.7709(3) A. Each silver(I) center is bonded to the two oxygen atoms of the THF molecules with a Ag-O bond distance of 2.307(3) A. TGA analysis showed that 1 loses two molecules of the coordinated solvent per molecular unit (1st one: 75-100 degrees, second one: 150-175 degrees C), whereas 2, 3, and 4 lose both volatile organic compounds (VOCs) and fluorinated ligands in a less well defined manner. Each complex loses both the fluorinated ligands and the VOCs by a temperature of about 325 degrees C to give a 1:1 gold/silver product. X-ray powder diffraction studies confirm that the reaction of vapors of VOCs with 1 in the solid state produce complete substitution of the ether molecules by the new VOC. The VOCs are replaced in the order CH3CN > Me2CO > THF > Et2O, with the ether being the easiest to replace. {Ag2(Et2O)2[Au(C6F5)2]2}n and {Ag2(THF)2[Au(C6F5)2]2} n both luminesce at room temperature and at 77 K in the solid state. Emission maxima are independent of the excitation wavelength used below about 500 nm. Emission maxima are obtained at 585 nm (ether) and 544 nm (THF) at room temperature and at 605 nm (ether) and 567 nm (THF) at 77 K.

Silver nanoparticles: synthesis through chemical methods in solution and biomedical applications

AbstractChemical methods provide an easy way to synthesize silver nanoparticles (Ag NPs) in solution. These metal nanoparticles have a great potential for biomedical applications as an antibacterial, antifungal, and antiviral agent or in wound healing. The adjustment of the parameters involved in these reactions permits a precise control over the size, shape, monodispersity, and the surfaces of the nanoparticles. These nanoparticles are being used in the design of new hybrid organic-inorganic or inorganic nanomaterials for biomedical applications.

New palladium(II) and platinum(II) complexes with 9-aminoacridine: structures, luminiscence, theoretical calculations, and antitumor activity.

The new complexes [Pd(dmba)( N10-9AA)(PPh 3)]ClO 4 ( 1), [Pt(dmba)( N9-9AA)(PPh 3)]ClO 4 ( 2), [Pd(dmba)( N10-9AA)Cl] ( 3), and [Pd(C 6F 5)( N10-9AA)(PPh 3)Cl] ( 4) (9-AA = 9-aminoacridine; dmba = N,C-chelating 2-(dimethylaminomethyl)phenyl) have been prepared. The crystal structures have been established by X-ray diffraction. In complex 2, an anagostic C-H...Pt interaction is observed. All complexes are luminescent in the solid state at room temperature, showing important differences between the palladium and platinum complexes. Complex 2 shows two structured emission bands at high and low energies in the solid state, and the lifetimes are in agreement with excited states of triplet parentage. Density functional theory and time-dependent density functional theory calculations for complex 2 have been done. Values of IC 50 were also calculated for the new complexes 1- 4 against the tumor cell line HL-60. All of the new complexes were more active than cisplatin (up to 30-fold in some cases). The DNA adduct formation of the new complexes synthesized was followed by circular dichroism and electrophoretic mobility. Atomic force microscopy images of the modifications caused by the complexes on plasmid DNA pB R322 were also obtained.

Experimental and theoretical evidence of the first Au(I)⋯Bi(III) interaction

Complex [Au(C6F5)2][Bi(C6H4CH2NMe(2)-2)2] displays the first example of an interaction between Au(I) and Bi(III), the nature of which is shown to be consistent with the presence of a high ionic contribution (79%) and a dispersion type (van der Waals) interaction (21%).

Golden Metallopolymers with an Active T1 State via Coordination of Poly(4-vinyl)pyridine to Pentahalophenyl-Gold(I) Precursors

Brightly phosphorescent gold-based metallopolymers have been synthesized by reaction of nonluminescent reactants comprised of the commercially available polymer PVP = poly(4-vinylpyridine) and the Au(I) precursors [Au(C(6)X(5))THT] (X = F or Cl; THT = tetrahydrothiophene). The metallopolymer products exhibit remarkable photoluminescence properties including high solid-state quantum yield (up to 0.63 at RT) and coarse- and fine-tuning to multiple phosphorescence bands across the visible spectrum via luminescence thermochromism and site-selective excitation. The emissions are caused by intrachain and interchain aurophilic interactions between the linear Au(I) complexes in the metallopolymers. This investigation provides further manifestations of interesting chemistry and photophysics in N-heterocyclic coordination compounds of Au(I) by expansion from the small-molecule to the metallopolymer regime. The spectroscopic and material properties of the new class of metallopolymers are desirable for future studies that will utilize them as emitters for photonic applications such as polymer light-emitting diodes and sensors.

Unsupported Au(I)⋯Cu(I) interactions: influence of nitrile ligands and aurophilicity on the structure and luminescence

The synthesis, structural characterization and the study of the photophysical properties of complexes [AuCu(C6F5)2(N[triple bond]C-CH3)2] 1, [AuCu(C6F5)2(N[triple bond]C-Ph)2]2 2, and [AuCu(C6F5)2(N[triple bond]C-CH=CH-Ph)2] 3 have been carried out. The crystal structures of complexes 1-3 consist of dinuclear Au-Cu units built from mediated metallophilic Au(I)...Cu(I) interactions. In the case of complex 2 two dinuclear units interact via an aurophilic interaction leading to a tetranuclear Cu-Au-Au-Cu arrangement. Complex 2 is brightly luminescent in solid state at room temperature and at 77 K with a lifetime in the nanoseconds range, while complexes 1 and 3 do not display luminescence under the same conditions. The presence of the aurophilic interaction in complex 2 seems to be responsible for the blue luminescence observed. DFT and time-dependent DFT calculations agree with the experimental results and support the idea that the origin of the luminescence of these complexes arise from orbitals located in the interacting metals.

Amalgamating at the molecular level. A study of the strong closed-shell Au(I)···Hg(II) interaction.

Complex {[Hg(C(6)F(5))(2)][Au(C(6)F(5))(PMe(3))](2)}(n)2 displays unsupported Au(I)···Hg(II) and Au(I)···Au(I) interactions. Its crystal structure displays a polymeric -(Au-Hg-Au-Au-Hg-Au)(n)- disposition. Ab initio calculations show very strong Au(I)···Hg(II) and Au(I)···Au(I) closed-shell interactions of -73.3 kJ mol(-1) and -57.0 kJ mol(-1), respectively, which have a dispersive (van der Waals) nature and are strengthened by large relativistic effects (>20%).

Multiple Evidence for Gold(I)⋅⋅⋅Silver(I) Interactions in Solution

[AuAg3(C6F5)(CF3CO2)3(CH2PPh3)]n (2) was prepared by reaction of [Au(C6F5)(CH2PPh3)] (1) and [Ag(CF3CO2)] (1:3). The crystal structures of complexes 1 and 2 were determined by X-ray diffraction, and the latter shows a polymeric 2D arrangement built by Au...Ag, Ag...Ag, and Ag...O contacts. The metallophilic interactions observed in 2 in the solid state seem to be preserved in concentrated THF solutions, as suggested by EXAFS, pulsed-gradient spin-echo NMR, and photophysical studies, which showed that the structural motif [AuAg3(C6F5)(CF3CO2)3(CH2PPh3)] is maintained under such conditions. Time-dependent DFT calculations agree with the experimental photophysical energies and suggest a metal-to-ligand charge-transfer phosphorescence process. Ab initio calculations give an estimated interaction energy of around 60 kJ mol(-1) for each Au...Ag interaction.

A Study of the Interactions in an Extended Unsupported Gold-Silver Chain

The complex [Ag(Py)3][Au(C6F5)2]·Py (1) (Py = pyridine) has been prepared by the reaction of NBu4[Au(C6F5)2] with AgClO4 in the presence of pyridine. The crystallographic measurements indicate the presence of an extended unsupported one-dimensional chain of alternating gold and silver atoms. This arrangement is due to the formation of molecular Au−Ag ion pairs, to the π-stacking of C6F5 and pyridine arene ligands and to the packing effects that lead to molecular ion pairs at short distance. Theoretical calculations based on approximate experimental distances and angles reveal the presence of both metallophilic AuI−AgI and aromatic C6F5-pyridine interactions. From a theoretical point of view the nature of the intermetallic attraction arises from both an ionic contribution and from dispersion-type correlation effects; the aromatic interaction is mainly due to dispersion-type correlation effects.