Mono- and Dinuclear Gold(I) Coumarin Complexes: Luminescence Studies and Singlet Oxygen Production.

The 4-(thiolmethyl)-7-(diethylamino)-2H-chromen-2-one ligand has been synthesized and used as chromophore in several mono- and dinuclear gold(I) compounds that contain a phosphane at the second coordination position. Four final products were able to obtain in pure form containing one coumarin and one phosphane ligand in the case of PTA (1,3,5-triaza-7-phosphatricyclo[3.3.1.13.7]decane) and PPh3 (triphenylphosphine); one coumarin and two gold(I)-phosphane groups in the case of phosphane=DAPTA (3,7-diacetyl-1,3,7-triaza-5-phosphabicyclo[3.3.1]nonane) and two coumarin and two gold(I) atoms in the case of phosphane=DPEphos (bis[(2-diphenylphosphino)phenyl]ether), when it was used a diphosphane. Other diphosphane ligands used were not able to give the desired products in pure form. The luminescent properties of the compounds are governed by the fluorescence of the coumarin moiety in all compounds both for measurements carried out in solution and also immobilized in PMMA organic matrix. Phosphorescence emission can be detected in all cases at 77 K both for the uncoordinated coumarin ligand and the gold(I) derivatives, being more favoured in the presence of the gold(I) heavy atom. The compounds have been used as photosensitizers to generate 1 O2 with moderate quantum yields values.

Using Room Temperature Phosphorescence of Gold(I) Complexes for PAHs Sensing.

The synthesis of two new phosphane-gold(I)-napthalimide complexes has been performed and characterized. The compounds present luminescent properties with denoted room temperature phosphorescence (RTP) induced by the proximity of the gold(I) heavy atom that favors intersystem crossing and triplet state population. The emissive properties of the compounds together with the planarity of their chromophore were used to investigate their potential as hosts in the molecular recognition of different polycyclic aromatic hydrocarbons (PAHs). Naphthalene, anthracene, phenanthrene, and pyrene were chosen to evaluate how the size and electronic properties can affect the host:guest interactions. Stronger affinity has been detected through emission titrations for the PAHs with extended aromaticity (anthracene and pyrene) and the results have been supported by DFT calculation studies.

Kinetico-mechanistic insights on the assembling dynamics of allyl-cornered metallacycles: the Pt-Npy bond is the keystone.

The square-like homo- and heterometallamacrocycles [{Pd(η(3) -2-Me-C3 H4 )(L(n) )2 }2 {M(dppp)}2 ](CF3 SO3 )6 (dppp=1,3-bis(diphenylphosphino)propane) and [{Pd(η(3) -2-Me-C3 H4 )(L(1) )2 }2 {M(PPh3 )2 }2 ](CF3 SO3 )6 [py=pyridine, M=Pd, Pt, L(n=) 4-PPh2 py (L(1) ), 4-C6 F4 PPh2 py (L(2) )] containing allyl corners were synthesised by antisymbiotic self-assembly of the different palladium and platinum metallic corners and the ambidentate N,P ligands. All the synthesised assemblies displayed a complex dynamic behaviour in solution, the rate of which is found to be dependent on the electronic and/or steric nature of the different building blocks. A kinetico-mechanistic study by NMR line shape analysis of the dynamics of some of these assemblies was undertaken in order to determine the corresponding thermal activation parameters. Both an enhanced thermodynamic stability and slower dynamics were observed for platinum-pyridine-containing species when compared with their palladium analogues. Time-dependent NMR spectroscopy in combination with ESI mass spectrometry was used to study the exchange between the assemblies and their building blocks, as well as that occurring between different metallamacrocycles. Preliminary studies were carried out on the activity of some of the metallamacrocyclic compounds as catalytic precursors in the allylic substitution reaction, and the results compared with that of the monometallic allylic corner [Pd(η(3) -2-Me-C3 H4 )(L(1) )2 ](+) .

A General Approach To Fabricate Fe3O4 Nanoparticles Decorated with Pd, Au, and Rh: Magnetically Recoverable and Reusable Catalysts for Suzuki C-C Cross-Coupling Reactions, Hydrogenation, and Sequential Reactions.

A facile strategy has been explored for loading noble metals onto the surface of ferrite nanoparticles with the assistance of phosphine-functionalized linkers. Palladium loading is shown to occur with participation of both the phosphine function and the surface hydroxyl groups. Hybrid nanoparticles containing simultaneously Pd and Au (or Rh) are obtained by successive loading of metals. Similarly, ferrite nanoparticles decorated with Pd, Au, and Rh have also been formed by using the same strategy. The catalytic properties of the new nanoparticles are evidenced in processes such as reduction of 4-nitrophenol or hydrogenation of styrene. Besides, the sequential process involving a cross-coupling reaction followed by reduction of 1-nitrobiphenyl has been successfully achieved by employing Pd/Au decorated nanoferrite particles.

Improved thermal stability of oxide-supported naked gold nanoparticles by ligand-assisted pinning.

We report a method to improve the thermal stability, up to 900 °C, of bare-metal (naked) gold nanoparticles supported on top of SiO(2) and SrTiO(3) substrates via ligand-assisted pinning. This approach leads to monodisperse naked gold nanoparticles without significant sintering after thermal annealing in air at 900 °C. The ligand-assisted pinning mechanism is described.

Synthetic strategies for the surface functionalisation of gold nanoparticles with metals and metal clusters.

The reaction of the new ditopic thiol-phosphine compound HS(CH(2))(11)OOCC(6)H(4)PPh(2) (L) with an excess of dodecanethiol-protected gold nanoparticles gave the asymmetric gold complex [CH(3)(CH(2))(11)SAuPPh(2)C(6)H(4)COO(CH(2))(11)SH] (4), but no phosphine-protected gold nanoparticles were formed. However, by blocking the phosphine function in L with metal fragments, we have been able to produce gold nanoparticles functionalised with AuCl- and cluster [Fe(2)(CO)(7)Au] units on the surface by the method of ligand-place exchange reaction.

Identification of a potent activator of Akt phosphorylation from a novel series of phenolic, picolinic, pyridino, and hydroxamic zinc(II) complexes.

The discovery of small-molecule modulators of signaling pathways is currently a particularly active area of research. We aimed at developing unprecedented metal-based activators of Akt signaling which can potentially find applications as tools for regulating glucose metabolism downstream of Akt or serve as lead structures for developing antidiabetic drugs. In this context, a highly diverse library of 11 new zinc(II) complexes with phenolic, picolinic, pyridino, and hydroxamic ligands, all containing features beneficial for medicinal purposes, was prepared and screened in an assay that detected levels of phospho-Akt in lysates from NIH3T3 cells after treatment with the compounds. The complexes featuring hydroxamic ligands were found to be the most prominent activators of Akt among the molecules prepared, with the most efficient compound acting at submicromolar concentrations. Further characterization revealed that this compound induces phosphorylation of the Akt downstream effector glycogen synthase kinase 3ß, but does not act as an inhibitor of tyrosine phosphatases or PTEN.