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The research leading to these results has received funding from Laserlab-Europe (grant agreement 284464, EC's Seventh Framework Programme). The authors are grateful to the Ministry of Economy, Industry and Competitiveness of Spain (AEI/FEDER, UE Project CTQ2016-76120-P). This work was also supported by the Associated Laboratory for Sustainable Chemistry, Clean Processes and Technologies, LAQV, which is financed by national funds from FCT/MEC (UID/QUI/50006/2013) and cofinanced by the ERDF under the PT2020 Partnership Agreement (POCI-01-014S-FEDER-007265). We also acknowledge funding from FEDER (Fundo Europeu de Desenvolvimento Regional) through COMPETE (Programa Operacional Factores de Competitividade). The Coimbra Chemistry Centre is supported by the Fundacao para a Ciencia e a Tecnologia (FCT), Portuguese Agency for Scientific Research, through the programme UID/QUI/UI0313/2013. J.P. acknowledges the project SunStorage Harvesting and storage of solar energy", for financial support, reference POCI-01-0145-FEDER-016387, funded by European Regional Development Fund (ERDF), through COMPETE 2020 - Operational Programme for Competitiveness and Internationalization (OPCI), and by national funds, through FCT. An electronic spectral and photophysical characterization of three gold(I) complexes containing heterocyclic chromophores differing in the number and arrangement of pyridine rings (pyridine, bipyridine, and terpyridine, with the acronyms pD, bD, and tD respectively) was performed. Quantum yields of fluorescence, internal conversion and triplet state formation, together with the rate constants for singlet to triplet intersystem crossing, S1 ∼ ∼ ∼ S0 internal conversion and fluorescence were measured in order to equate the impact of fast triplet state formation on the amount of triplets formed. The results showed a correlation between the increase on the measured decay values of S1 (leading to the main formation of T1) and the increase in the charge transfer (CT) character of the lowest energy transition, as evaluated from the orthogonality of the frontier orbitals. The measured triplet state quantum yields range from ∼50-60% to 70%, whereas the intersystem crossing rate constants differ by almost 2 orders of magnitude, from 9.4 × 109 s-1 for tD to 8.1 × 1011 s-1 for bD. This constitutes an evidence for the existence of a correlation between the intersystem crossing and the internal conversion mechanisms. authorsversion published

A series of 4-ethynylaniline gold(I) complexes containing monophosphane (1,3,5-triaza-7-phosphaadamantane (pta; 2), 3,7-diacetyl-1,3,7-triaza-5-phosphabicyclo[3.3.1]nonane (3), and PR3 , with R=naphthyl (4), phenyl (5), and ethyl (6)) and diphosphane (bis(diphenylphosphino)acetylene (dppa; 7), trans-1,2-bis(diphenylphosphino)ethene (dppet; 8), 1,2-bis(diphenylphosphino)ethane (dppe; 9), and 1,3-bis(diphenylphosphino)propane (dppp; 10)) ligands have been synthesized and their efficiency against tumor cells evaluated. The cytotoxicity of complexes 2-10 was evaluated in human colorectal (HCT116) and ovarian (A2780) carcinoma as well as in normal human fibroblasts. All the complexes showed a higher antiproliferative effect in A2780 cells, with the cytotoxicity decreasing in the following order 5>6=9=10>8>2>4>7>3. Complex 4 stands out for its very high selectivity towards ovarian carcinoma cells (IC50 =2.3 μm) compared with colorectal carcinoma and normal human fibroblasts (IC50 >100 μm), which makes this complex very attractive for ovarian cancer therapy. Its cytotoxicity in these cells correlates with the induction of the apoptotic process and an increase of intracellular reactive oxygen species (ROS). The effects of the nuclearity, rigidity, and solubility of these complexes on their biological activity were also analyzed. X-ray crystal structure determination allowed the identification of short N-H⋅⋅⋅π contacts as the main driving forces for the three-dimensional packing in these molecules.

We report the synthesis of an unprecedent mono-gold(I) phosphine complex based on a 'two wall' aryl-ethynyl extended calix[4]pyrrole. We describe and compare the binding properties of the parent 10α,20α-bis-aryl-ethynyl calix[4]pyrrole ligand and the prepared organometallic compound as receptors for tetraalkylammonium chloride salts in dichloromethane and acetone solutions. We describe the results of 1H NMR, UV-vis titrations and isothermal titration calorimetry (ITC) experiments in DCM and acetone solution, aiming at thermodynamically characterize the formed complexes. The obtained results indicate a noticeable decrease in the binding affinity of the chloride for the mono-gold(I) receptor 1 compared to the parent ligand 2. The increase in the negative value of the electrostatic surface potential at the center of the aromatic ring of the gold(I) meso-aryl-ethynyl substituent serves to explain the observed results and the presence in solution of the chloride complex of 1 as a mixture of two conformers.

Different gold microstructures have been synthesized by using supramolecular gold(I) organometallic compounds as templates and Ag nanoparticles as reducing agents. The use of fibers resulting from supramolecular assemblies of neutral gold(I) compounds gives rise to the formation of microrods. The use of supramolecular assemblies from ionic molecules results in spherical or square-based prism gold microstructures, depending on the shape of the supramolecular gold(I) precursor assembly. In addition to temperature and reaction time, solvents exert a strong influence on the formation and morphology of gold structures, as borne out by the example that well-defined star-like morphologies have been obtained in chloroform.

The synthesis of two dinuclear ionic complexes with chemical formula [Au(PR 3 ) 2 ][Au(C ≡ CC 5 H 4 N-4) 2 ] that contain the water soluble phosphines, PR 3 , PTA (1, 3,5-triaza-7-phosphaadamantane, 1 ) and DAPTA (3,7-diacetyl-1,3,7-triaza-5-phosphabicyclo[3.3.1]nonane, 2 ) is herein described. The differences on their intermolecular reorganization have been analyzed and compared with the previously reported for the neutral complexes [Au(PR 3 )(C ≡ CC 5 H 4 N-4)]. It has been evidenced that the reorganization of the ligands giving rise to the dinuclear ionic complexes produces a complete change in the properties giving rise to Au⋯Au intermolecular assemblies. These aurophilic contacts are the responsible for the resulting luminescence which is not displayed for the parent compounds [Au(PR 3 ) 2 ]Cl and [PPh 4 ][Au(C ≡ CC 5 H 4 N-4) 2 ]. Compounds 1 and 2 were made react with three different silver salts (nitrate, triflate and hexafluorophosphate) giving rise to 1:1 heterometallic assemblies with some changes both on the wavelength and emission intensity.

A series of alkynyl gold(I) tri and tetratopic metallaligands of the type [Au3(CuC-R)3(μ3-triphosphane)] (R = 2,2'-bipyridin-5-yl or C10H7N2, 2,2':6',2''-terpyridin-4-yl or C15H10N3; triphosphane = 1,1,1-tris(diphenylphosphanyl) ethane or triphos, 1,3,5-tris(diphenylphosphanyl)benzene or triphosph) and [Au4(CuC-R)4 (μ4-tetraphosphane)] (R = C10H7N2, C15H10N3; tetraphosphane = tetrakis(diphenylphosphanylmethyl)methane or tetraphos, 1,2,3,5-tetrakis(diphenylphosphanyl)benzene or tpbz, tetrakis(diphenylphosphaneylmethyl)-1,2- ethylenediamine or dppeda) were obtained in moderate to good yields. All complexes could be prepared by a Q4 reaction between the alkynyl gold(I) polymeric species [Au(CuC-R)]n and the appropriate polyphosphane. An alternative strategy that required the previous synthesis of the appropriate acetylacetonate precursors [Aun(acac)n(μn-polyphosphane)] ('acac method') was assayed, nevertheless only the polyacac derivatives [Au3(acac)3(μ3-triphosphane)] (triphosphane = triphos and triphosph) and [Au4(acac)4(μ4-tetraphos)] could be isolated and characterized. All compounds were characterized by IR, multinuclear NMR spectroscopy and ESI (+) mass spectrometry. The X-ray crystal structure of complexes [Au4(CuC-C10H7N2)4(μ4-tetraphos)] and [Au4(CuC-C10H7N2)4(μ4-tpbz)] showed the involvement of all the gold atoms in close intramolecular Au⋯Au contact as well as intermolecular π stacking interactions between the aromatic rings of the polypyridyl ligands. The photophysical properties of the synthesized compounds were carefully studied and used as a probe of their possible use as multidentate ligands for Cu(I) and Zn(II). The UV-Vis speciation studies of the complexation reactions were conducted via metal titration and, in most cases the dangling units of the ligand were found to behave in a fairy independent manner. While in the case of Cu(I) multiple equilibria exist in solution a single complex is detected for Zn(II) under the conditions studied.

The synthesis of three gold(I) tripodal complexes derived from tripropargylamine and containing the water soluble phosphines PTA (1, 3,5-triaza-7-phosphaadamantane), DAPTA (3,7-diacetyl-1,3,7-triaza-5-phosphabicyclo[3.3.1]nonane) and TPPTS (triphenylphosfine-3,3',3''-trisulfonic acid trisodium salt) is here described. The three complexes are observed to give rise to the formation of supramolecular aggregates in water and very long fibers. This property has been analyzed by means of 1H-NMR spectroscopy at different concentrations and SAXS. The results point out the important role of the phosphine moieties as the main enthalpic or entropic contribution in the resulting Gibbs energy of aggregates formation. The tripodal structure of the three complexes together with the presence of gold(I) atoms make them ideal candidates to interact with hydrophobic molecules also in water. For this, the interaction with pyrene in this solvent has been evaluated with successful results in all three complexes. The highest association constant corresponds to 2 as the host. DFT studies indicates the location of pyrene in the tripodal cavity as the most stable conformation. The interaction with pyrene has been additionally studied within cholate hydrogel matrixes pointing out the stability of the resulting host:guest adducts in the different medium.

The gold complexes [Au(4-pyridylethynyl)(PTA)] and [Au(4-pyridylethynyl)(DAPTA)] (PTA = 1,3,5-triaza-7-phosphaadamantane; DAPTA = 3,7-diacetyl-1,3,7-triaza-5-phosphabicyclo[3.3.1]nonane) were used as host in molecular recognition processes of sodium hexametaphosphate (HMP) and a single-stranded 24-long oligonucleotide. Experiments were performed by absorption titrations and looking at the resulting host:guest adducts by polarised optical, fluorescence and scanning electron microscopy. The resulting information indicates that different types of interactions are present with the two different guest molecules. In the case of HMP, the compounds aggregate giving rise to larger structures, favouring exciton splitting coupling and the formation of head to tail interactions. In the case of oligonucleotide studies, the formation of smaller supramolecular structures is observed, with less contribution of aurophilic contacts and organised in a parallel way (head to head interactions organised by the presence of the oligonucleotide).

The synthesis of the cationic gold(i) complexes [Au(C[triple bond, length as m-dash]CC5H4N)(CH3-PTA)]X (X = I, 1; X = OTf, 4), [Au(C[triple bond, length as m-dash]CC5H4N-CH3)(PTA)]X (X = I, 2; X = OTf = 5; PTA = 1,3,5-triaza-7-phosphatricyclo[3.3.1.13.7]decane) and [Au(C[triple bond, length as m-dash]CC5H4N-CH3)(DAPTA)]X (X = I, 3; X = OTf = 6, DAPTA = 3,7-diacetyl-1,3,7-triaza-5-phosphabicyclo[3.3.1]nonane) results in cationic complexes with unexpected supramolecular assemblies in water ranging from rod-like structures (1) to vesicles (2 and 3) and square-like structures (5 and 6). These morphologies are completely different from the fibers previously obtained with their parent neutral complexes [Au(C[triple bond, length as m-dash]C5H4N)(PTA)] and [Au(C[triple bond, length as m-dash]C5H4N)(DAPTA)]. Nevertheless, the introduction of triflate as a counterion in 1 (complex 4) gives rise to the formation of a highly soluble complex in water which does not display any significant aggregation in solution. These results reveal the importance of the introduction of a positive charge on global supramolecular assemblies and how the counterion can also modify the resulting package. Interestingly, we have also proved that the aggregation of complexes 2, 3, 5 and 6 is also affected by the solvent with direct influence on their absorption and emission properties and the global morphology of the aggregates.

The reaction of the gold polymers containing bipyridyl and terpyridyl units, [Au(C≡CC15H10N3)]n and [Au(C≡CC10H7N2)]n, with the water-soluble phosphines 1,3,5-triaza-7-phosphatricyclo[3.3.1.13.7]decane and 3,7-diacetyl-1,3,7-triaza-5-phosphabicyclo[3.3.1]nonane gives rise to the formation of four gold(I) alkynyl complexes that self-assemble in water (H2O) and dimethyl sulfoxide (DMSO), through different intermolecular interactions, with an impact on the observed luminescence displayed by the supramolecular assemblies. A detailed analysis carried out by NMR studies performed in different DMSO/deuterated H2O mixtures indicates the presence of two different assembly modes in the aggregates: (i) chain assemblies, which are based mainly on aurophilic interactions, and (ii) stacked assemblies, which are based on Au···π and π···π interactions. These different supramolecular environments can also be detected by their intrinsic optical properties (differences in absorption and emission spectra) and are predicted by the changes in the relative binding energy from density functional theory calculations carried out in DMSO and H2O. Small-angle X-ray scattering (SAXS) experiments performed in the same mixture of solvents are in agreement with the formation of aggregates in all cases. The aromatic units chosen, bipyridine and terpyridine, allow the use of external stimuli to reversibly change the aggregation state of the supramolecular assemblies. Interaction with the Zn2+ cation is observed to disassemble the aggregates, while encapsulating agents competing for Zn2+ complexation revert the process to the aggregation stage, as verified by SAXS and NMR. The adaptive nature of the supramolecular assemblies to the metal-ion content is accompanied by significant changes in the absorption and emission spectra, signaling the aggregation state and also the content on Zn2+. © 2017 American Chemical Society., The authors are grateful to the Ministry of Economy, Industry and Competitiveness of Spain (AEI/FEDER, UE Projects CTQ2016-76120-P, CTQ2015-65040-P, and CTQ2015-70117-R). This work was also supported by the Associated Laboratory for Sustainable Chemistry, Clean Processes and Technologies, LAQV, which is financed by national funds from FCT/MEC (UID/QUI/50006/2013) and cofinanced by the ERDF under the PT2020 Partnership Agreement (POCI-01-0145-FEDER-007265). The IQAC NMR Facility 500 MHz spectrometer and cryoprobe were funded by the CSIC13-4E-2076 MINECO-FEDER grant. SAXS experiments were performed at the NCD-BL11 beamline of the ALBA Synchrotron Light Facility in collaboration with the ALBA staff. A.J.M. thanks the FCT for a postdoctoral grant (SFRH/ BPD/69210/2010). This research was supported by a Marie Curie Intra European Fellowship within the 7th European Community Framework Programme (to R.G.). We also thank L. Gimeńez and I. Brea for their help on the synthesis of the ligands.

The reaction of [Au(C6F5)(tht)] (tht = tetrahydrothiophene) with 1,3,5-triaza-7-phosphaadamantane (PTA) and 3,7-diacetyl-1,3,7-triaza-5-phosphabicyclo[3.3.1]nonane (DAPTA) leads to the formation of [Au(C6F5)(phosph)] (phosph = PTA, 1; phosph = DAPTA, 2). The compounds are slightly soluble in water and aggregate at higher concentrations, giving rise to the formation of needle- and rodlike structures (1) and well-organized spherical aggregates (2). Compounds 1 and 2 were reacted with AgPF6, giving rise to the formation in all cases of luminescent water-soluble 1:1 Au···Ag heterometallic complexes, as evidenced by X-ray crystal structure determination. The use of different silver salts that differ on the counterion induces changes in the resulting luminescence and aggregation morphology.

Gold(I) complexes are an increasing area of investigation due to the possibility of giving rise to supramolecular aggregates with particular and morphologies that can be modulated together with their luminescent properties. A detailed study has been carried out for gold(I) complexes that self-assemble in aqueous medium (in pure water or in mixtures of water with organic solvents in different proportions). The majority of the examples reported until now are found in mixtures of water and DMSO, acetone, DMF or acetonitrile. The addition of cations to a solution of gold(I) complexes has been observed to show a direct impact on the resulting process of aggregation. The use of perhalogenated ligands together with isocyanide moieties should be denoted to promote the resulting self-organization. Nevertheless, other ligands like alkynyls or carbenes also promote self-assembly. A careful analysis of the data shows that aurophilic interactions have a key role in the formation of the resulting aggregates and in the enhancement of the luminescence (aggregation induced emission, AIE).

A new 2,7,10,15-tetraethynyldibenzo[g,p]chrysene ligand (1) and two tetranuclear gold(I) derivatives containing PPh3 (3) and PMe3 (4) phosphines were synthesized and characterized by 1H and 31P NMR, IR spectroscopy, and high-resolution mass spectrometry. The compounds were studied in order to analyze the effect of the introduction of gold(I) on the supramolecular aggregation and photophysical properties. Absorption and emission spectra displayed broad bands due to the establishment of &pi, &pi, interactions as an indication of intermolecular contacts and the formation of aggregates. A decrease of the recorded quantum yield (QY) of the gold(I) derivatives was observed compared to the uncomplexed ligand. The introduction of the complexes into poly methyl methacrylate (PMMA) and Zeonex 480R matrixes was analyzed, and an increase of the measured QY of 4 in Zeonex was observed. No phosphorescent emission was detected.

The spectroscopic properties of aggregates obtained from the hydrogelator [Au(4-pyridylethynyl)(PTA)] were studied in solvents of different polarities. Inspection of the absorption and emission spectra of diluted solutions showed that the singlet ground state of the monomeric species is sensitive to polarity and is stabilized in more polar solvents whereas the triplet excited state is rather insensitive to changes in polarity. The study of relatively concentrated solutions revealed the presence of new emission and excitation bands at 77 K that was attributed to the presence of different kinds of aggregates. Particularly interesting behaviour was revealed in water where aggregation is observed to be more efficient. For this, absorption, emission quantum yields and luminescence lifetimes of aqueous solutions at different concentrations were investigated in more detail. These data permitted one to correlate the increase of nonradiative and radiative rate constants of the low lying triplet emissive state with concentration, and therefore with the low limit concentration for aggregation, due to the shortening of the Au. Au average distances in the aggregates and consequent enhancement of the spin-orbit coupling in the system.

En aquesta tesi doctoral es descriu la síntesi i la caracterització de nanopartícules homo- i heterometàl•liques, així com la dels seus lligands estabilitzadors. A més, s’estudia el comportament catalític de les nanopartícules quan s’utilitzen com a materials catalítics en sí, i quan s’utilitzen com a suport d’altres entitats catalítiques. En una primera fase, s’ha detallat la síntesi i la caracterització de dendrons tipus carbosilà funcionalitzats al punt focal amb un grup tiol. Posteriorment, aquestes molècules s’han utilitzat com a agents estabilitzadors en la formació de nanopartícules d’or (AuNPs). Mitjançant el mètode bifàsic de Brust, s’obtenen les AuNPs estabilitzades amb els dendrons de generació zero i primera generació amb diàmetres de 2,5 i 2,6 nm, respectivament. Les AuNPs formades tenen una distribució uniforme i una estabilitat remarcable. D’altra banda, s’ha sintetitzat un compost model amb el que s’han estabilitzat AuNPs amb un diàmetre d’uns 2,7 nm. Fent ús d’un micromonòlit funcionalitzat amb nanopartícules d’or estabilitzades amb el dendró de primera generació (MFAu), s’ha assajat l’oxidació selectiva de CO en presència d’hidrogen, i s’ha comparat amb l’activitat de monòlits convencionals (MC). L’activitat del MFAu és més de dos ordres de magnitud superior a la del MC. En una segona fase, s’ha sintetitzat un lligand estabilitzador compost per una cadena tipus alcà funcionalitzada amb un grup tiol a un extrem i amb una piridina a l’altre. Mitjançant processos d’intercanvi a partir de nanopartícules d’or estabilitzades amb 1-hexantiol s’ha incorporat una quantitat controlada del lligand. La reacció entre les nanopartícules i els dímers [RhCl(cod)]2 i [RuCl2(p-cimè)]2 ha permès la incorporació de fragments metàl•lics a la perifèria. S’han estudiat les reaccions catalítiques d’isomerització del geraniol i hidrogenació de l’1-octè amb les AuNPs que contenien ruteni i rodi, respectivament. Es creu que els processos de degradació i aglomeració de les nanopartícules observats són els causants de les baixes conversions obtingudes. En una tercera fase, s’ha descrit la formació de nanopartícules de magnetita funcionalitzades amb lligands que contenen unitats fosfina (d’uns 13 nm de diàmetre), i s’ha analitzat la seva capacitat per carregar diferents complexos metàl•lics, així com la possibilitat dipositar-hi les nanopartícules metàl•liques corresponents. D’aquesta manera, s’ha aconseguit obtenir nanopartícules de magnetita amb nanopartícules de fins a tres metalls de transició diferents (Pd, Au i Rh) dipositades a la seva superfície. A més, la comparació de la càrrega de Pd obtinguda separadament sobre de les nanopartícules de magnetita funcionalitzada i de nanopartícules de magnetita nues, així com d’unes noves nanopartícules dissenyades expressament (nanopartícules de magnetita funcionalitzades amb unitats catecol), ha permès establir les vies d’incorporació del metall a les nanopartícules de magnetita. Altrament, s’ha demostrat en diversos processos catalítics el bon comportament catalític dels nous catalitzadors magnètics. També s’ha estudiat per primera vegada una reacció seqüencial one-pot, que implica en primer lloc la reacció d’acoblament creuat C-C Suzuki-Miyaura, entre el 1-bromo-4-nitrofenol i l’àcid fenilborònic, seguit de la reducció del grup nitro corresponent a amina. Per últim, s’ha intentat funcionalitzar AuNPs amb un lligand que conté un grup ditiocarbamat a un extrem i dos grups difenilfosfina a l’atre. Tot i que es creia que en un principi l’ús d’un grup ditiocarbamat enlloc d’un grup tiol solucionaria els problemes de degradació de les nanopartícules, vistos AuNPs estabilitzades amb lligands tiol-fosfina, s’ha comprovat que no és així: s’observa el desancoratge dels lligands i la precipitació d’or metàl•lic. La síntesi de complexos moleculars anàlegs ha permès corroborar que en l’estabilització de AuNPs amb aquest tipus de lligands, els grups fosfina es coordinen als àtoms d’or superficials i els arrenquen de les nanopartícules. Amb la idea d’obtenir un lligand versàtil, capaç d’estabilitzar AuNPs i coordinar fragments metàl•lics, s’ha sintetitzat un lligand que conté en un extrem un grup tiol i a l’altre un grup carboxilat. L’ús d’aquests lligands ha permès obtenir nanopartícules d’or i pal•ladi que contenen fragments metàl•lics de ruteni a la perifèria., In this thesis the synthesis and characterization of homo- and heterometallic nanoparticles, as well as the synthesis and characterization of their stabilizing agents, are described. Furthermore, the catalytic behavior of nanoparticles is studied when the nanoparticles are used as catalytic materials, and when they are used as a support for other catalytic entities. In a first step, the synthesis and characterization of carbosilane dendrons functionalized with a thiol group at the focal point have been detailed. Subsequently, these molecules have been used as stabilizing agents for the formation of gold nanoparticles (AuNPs). Using the Brust’s method, AuNPs stabilized with zero and first generation dendrons with diameters around 2.5 and 2.6 nm respectively, are obtained. Furthermore, a model compound has been synthesized and also used as a stabilizing agent for the formation of AuNPs (with an average diameter of 2.7 nm). The use functionalized micromonolith with gold nanoparticles stabilized with the first generation dendron (MFAu) was tested for the selective oxidation of CO in the presence of hydrogen, and compared with conventional monoliths’ activity (MC). MFAu activity proves to be two orders of magnitude higher than the MC. In a second step, it has been synthesized a stabilizing ligand with a chain alkane functionalized with a thiol and a pyridine group. The ligand was bonded to previous AuNPs stabilized with 1-hexanethiol. The reaction between the nanoparticles formed and the dimers [RhCl(cod)]2 and [RuCl2(p-cymene)]2 allows the incorporation of metal fragments in the periphery of the nanoparticle. The catalytic isomerization of geraniol and the hydrogenation of 1-octene have been studied using AuNPs containing ruthenium and rhodium, respectively. In a third step, it has been described the formation of magnetite nanoparticles functionalized with ligands containing phosphine units (with an averga diameter of 13 nm), and it has been analyzed firstly, their ability to coordinate with different metal complexes, and secondly, the possibility of depositing the corresponding metal nanoparticles. Thus, we have synthesized nanoparticle magnetite nanoparticles with up to three different transition metals (Pd, Au and Rh) deposited on its surface. The good catalytic activity of the new magnetic catalysts has been demonstrated in various catalytic processes. Finally, the possibility of obtaining AuNPs functionalized with a dithiocarbamate ligand bearing diphenylphosphine (DTC) groups has been tested. However, the AuNPs were not stable: the detachment of DTC ligands and precipitation of metallic gold were observed. With the idea of obtaining a versatile ligand, capable of stabilizing AuNPs and coordinating metal fragments, it has been synthesized a ligand containing a thiol and a carboxylate group. Using these ligands it has been possible to synthesize gold and palladium nanoparticles containing ruthenium metal fragments in the periphery.