Heterometallic Au(I)–Cu(I) Clusters : Luminescence Studies and 1O2 Production

Two different organometallic gold(I) compounds containing naphthalene and phenanthrene as fluorophores and 2-pyridyldiphenylphosphane as the ancillary ligand were synthesized (compounds 1 with naphthalene and 2 with phenanthrene). They were reacted with three different copper(I) salts with different counterions (PF6–, OTf–, and BF4–; OTf = triflate) to obtain six Au(I)/Cu(I) heterometallic clusters (compounds 1a–c for naphthalene derivatives and 2a–c for phenanthrene derivatives). The heterometallic compounds present red pure room-temperature phosphorescence in both solution, the solid state, and air-equilibrated samples, as a difference with the dual emission recorded for the gold(I) precu…

Polypyridyl-functionalizated alkynyl gold(i) metallaligands supported by tri- and tetradentate phosphanes

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(Cu…

The Important Role of the Nuclearity, Rigidity, and Solubility of Phosphane Ligands in the Biological Activity of Gold(I) Complexes

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 hi…

Luminescent alkynyl-gold(i) coumarin derivatives and their biological activity

The synthesis and characterization of three propynyloxycoumarins are reported in this work together with the formation of three different series of gold(i) organometallic complexes. Neutral complexes are constituted by water soluble phosphines (PTA and DAPTA) which confer water solubility to them. The X-ray crystal structure of 7-(prop-2-in-1-yloxy)-1-benzopyran-2-one and its corresponding dialkynyl complex is also shown and the formation of rectangular dimers for the gold derivative in the solid state can be observed. A detailed analysis of the absorption and emission spectra of both ligands and complexes allows us to attribute the luminescent behaviour to the coumarin organic ligand. More…

Effect of Gold(I) on the Room-Temperature Phosphorescence of Ethynylphenanthrene.

The synthesis of two series of gold(I) complexes containing the general formulae PR 3 ‐Au‐C≡C‐phenanthrene (PR 3 = PPh 3 ( 1a / 2a ), PMe 3 ( 1b / 2b ), PNaph 3 ( 1c / 2c )) or (diphos)(Au‐C≡C‐phenanthrene) 2 (diphos = 1,1‐ bis (diphenylphosphino)methane, dppm ( 1d / 2d ); 1,4‐ bis (diphenylphosphino)butane, dppb ( 1e / 2e )) have been synthesized. The two series differ on the position of the alkynyl substituent on the phenanthrene chromophore, being at the 9‐position (9‐ethynylphenanthrene) for the L1 ‐series and at the 2‐position (2‐ethynylphenanthrene) for the L2 ‐series. The compounds have been fully characterized by 1 H and 31 P NMR and IR spectroscopy, mass spectrometry and single cry…

Toward Near-Infrared Emission in Pt(II)-Cyclometallated Compounds: From Excimers’ Formation to Aggregation-Induced Emission

Two series of Pt(II)-cyclometallated compounds containing N^C^N tridentate and alkynyl-chromophore ligands have been synthesized and structurally characterized. The N^C^N ligands differ on the presence of R1 = H or F in the central aromatic ring, while six different chromophores have been introduced to the alkynyl moiety. Single-crystal X-ray structures for some of the compounds reveal the presence of weak intermolecular contacts responsible for the formation of some dimers or aggregates. The photophysical characterization shows the presence of two emission bands in solution assigned to the 3π–π* transition from the N^C^N ligands mixed with 3MLCT/3ILCT transitions (higher energy band) in de…

Base-assisted synthesis of 4-pyridinate gold(I) metallaligands: a study of their use in self-assembly reactions

Made available in DSpace on 2021-06-25T12:16:58Z (GMT). No. of bitstreams: 0 Previous issue date: 2021-05-06 Ministerio de Economia y Competitividad (MINECO/FEDER) of Spain Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) The synthesis of di- and tritopic gold(I) metallaligands of the type [(Au4-py)(2)(mu(2)-diphosphane)] (diphosphane = bis(diphenylphosphanyl)isopropane or dppip (1), 1,2-bis(diphenylphosphanyl)ethane or dppe (2), 1,3-bis(diphenylphosphanyl)propane or dppp (3) and 1,4-bis(diphenylphosphanyl)butane or dppb (4)) and [(Au4-py)(3)(mu(3)-triphosphane)] (triphosphane = 1,1,1-tris(diphenylphosph…

Supramolecular interactions of hexacyanocobaltate(III) with polyamine receptors containing a terminal anthracene sensor

Abstract The fluorescence emission properties of a series of chemosensors containing a polyamine receptor bearing an anthracene signaling unit were studied. The fluorescence emission intensity is dependent on the protonation degree of the receptor, the fully protonated form exhibiting the highest emission intensity. By removing protons from the nitrogens a quenching effect can be observed, due to an electron-transfer from the amine to the excited fluorophore. The rate constant of the quenching process is exponentially dependent on the distance of the nitrogen from which the electron is transferred (β=0.6 A−1). The ability of the chemosensors for signaling anions was tested through the model…

Room-Temperature Phosphorescence and Efficient Singlet Oxygen Production by Cyclometalated Pt(II) Complexes with Aromatic Alkynyl Ligands

The synthesis of five novel cyclometalated platinum(II) compounds containing five different alkynyl-chromophores was achieved by the reaction of the previously synthesized Pt–Cl cyclometalated compound (1) with the corresponding RC≡CH by a Sonogashira reaction. It was observed that the spectral and photophysical characteristics of the cyclometalated platinum(II) complexes (Pt–Ar) are essentially associated with the platinum-cyclometalated unit. Room-temperature emission of the Pt–Ar complexes was attributed to phosphorescence in agreement with DFT calculations. Broad nanosecond (ns)-transient absorption spectra were observed with decays approximately identical to those obtained from the emi…

Intra- vs Intermolecular Aurophilic Contacts in Dinuclear Gold(I) Compounds: Impact on the Population of the Triplet Excited State.

Two series of dinuclear gold(I) complexes that contain two Au–chromophore units (chromophore = dibenzofurane or dimethylfluorene) connected through a diphosphane bridge that differs in the flexibility and length (diphosphane = dppb for 1,4-bis(diphenylphosphino)butane, DPEphos for bis[(2-diphenylphosphino)phenyl]ether, xanthphos for 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene, and BiPheP for 2,2′-bis(diphenylphosphino)-1,1′-biphenyl) have been synthesized and structurally characterized. Their photophysical properties have been carefully investigated, paying attention to the role of the presence, or absence, of aurophilic contacts and their nature (intra- or intermolecular character). Th…

Aggregation versus Biological Activity in Gold(I) Complexes. An Unexplored Concept

The aggregation process of a series of mono- and dinuclear gold(I) complexes containing a 4-ethynylaniline ligand and a phosphane at the second coordination position (PR3-Au-C≡CC6H4-NH2, complexes 1-5, and (diphos)(Au-C≡CC6H4-NH2)2, complexes 6-8), whose biological activity was previously studied by us, has been carefully analyzed through absorption, emission, and NMR spectroscopy, together with dynamic light scattering and small-angle X-ray scattering. These experiments allow us to retrieve information about how the compounds enter the cells. It was observed that all compounds present aggregation in fresh solutions, before biological treatment, and thus they must be entering the cells as a…

Front Cover: The Important Role of the Nuclearity, Rigidity, and Solubility of Phosphane Ligands in the Biological Activity of Gold(I) Complexes (Chem. Eur. J. 55/2018)

Luminescent supramolecular heterometallic macrocycles and their encapsulation on cholate gels

The metal complex formed by coordination of Zn(II) to 1,7-bis(4-methylpyridine)-4-(2- naphthylmethyl)-1,4,7-triazaheptane (ZnL2+) was reacted in aqueous solution with [Pd(NO3)2(en)] and [Pt(NO3)2(en)] salts to form the self-assembled heterometallic macrocycles [Zn2L2Pd2(en)2]8+ and [Zn2L2Pt2(en)2]8+, respectively. Pd(II) and Pt(II)- coordination modulates the original emission of ZnL2+ arising from the presence of the naphthalene chromophore and the formation of the macrocycles can be monitored due to the PET process occurring with coordination of Pd(II) and Pt(II) to the pyridine units of ZnL2+. Additionally, several studies reveal that these heteromacrocycles can be encapsulated in Zn(II)…

A coumarin based gold(i)-alkynyl complex: a new class of supramolecular hydrogelators.

A phosphine-gold(I)-alkynyl-coumarin complex, [Au{7-(prop-2-ine-1-yloxy)-1-benzopyran-2-one}(DAPTA)] (1), was synthesized and the formation of long luminescent fibers in solution was characterized via fluorescence microscopy and dynamic light scattering. The fibers presented strong blue and green luminescence, suggesting that the gold(I) in the complex increased intersystem crossing due to the heavy atom effect, resulting in a significant increase in triplet emission. The X-ray structure of the fibers indicates that both aurophilic, π–π interactions and hydrogen bonding contribute to their formation in aqueous solvents.

A coumarin based gold(I)-alkynyl complex: a new class of supramolecular hydrogelators

A phosphine-gold(I)-alkynyl-coumarin complex, [Au{7-(prop-2-ine-1-yloxy)-1-benzopyran-2-one}- (DAPTA)] (1), was synthesized and the formation of long luminescent fibers in solution was characterized via fluorescence microscopy and dynamic light scattering. The fibers presented strong blue and green luminescence, suggesting that the gold(I) in the complex increased intersystem crossing due to the heavy atom effect, resulting in a significant increase in triplet emission. The X-ray structure of the fibers indicates that both aurophilic, π–π interactions and hydrogen bonding contribute to their formation in aqueous solvents. peerReviewed

Supramolecular assemblies and photophysical properties of ionic homo- and heteronuclear metallophilic complexes

Abstract 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 conta…

Luminescent Pt-II and Pt-IV Platinacycles with Anticancer Activity Against Multiplatinum-Resistant Metastatic CRC and CRPC Cell Models

Platinum-based chemotherapy persists to be the only effective therapeutic option against a wide variety of tumours. Nevertheless, the acquisition of platinum resistance is utterly common, ultimately cornering conventional platinum drugs to only palliative in many patients. Thus, encountering alternatives that are both effective and non-cross-resistant is urgent. In this work, we report the synthesis, reduction studies, and luminescent properties of a series of cyclometallated (C,N,N')PtIV compounds derived from amine- imine ligands, and their remarkable efficacy at the high nanomolar range and complete lack of cross57 resistance, as an intrinsic property of the platinacycle, against multipl…

Gold(I)-doped films: new routes for efficient room temperature phosphorescent materials

The synthesis of four novel gold(I)-phosphane complexes coordinated to 9-phenanthrene chromophore has been carried out through the reaction of 9-phenanthreneboronic acid and the corresponding AuClPR3 (PR3 = PPh3 for triphenylphosphane (1a); 1,4-bis(diphenylphosphanyl)butane or dppb (2b); bis(diphenylphosphanyl)acetylene or dppa (2c); (AuCl)2(diphos) (diphos = bis(diphenylphosphanyl)methane or dppm (3)) sources. The X-ray crystal structures of compounds 1a and 2b show the existence of MOF-like intermolecular assemblies that contain empty inner cavities in the absence of aurophilic contacts. In contrast, the formation of a tetranuclear complex with intramolecular aurophilic interactions was e…

CCDC 1844227: Experimental Crystal Structure Determination

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CCDC 955661: Experimental Crystal Structure Determination

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CCDC 955660: Experimental Crystal Structure Determination

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