Search results for "ion chemistry"
showing 10 items of 254 documents
Fluorescent organometallic complexes : when the photovoltaic leads to theranostics
2013
The goal of my PhD thesis was to synthesize new molecules, which give access to fluorescentorganometallic complexes with interesting properties for photovoltaic and theranostic. In thisproject, several main points have been studied.The first part of this manuscript concerns the synthesis of new metallocene and metalloporphyrinsbasedorganometallic complexes to the design of solar cells. After a short introduction, wepresented the synthesis of titanium complexes and metalloporphyrins in the first chapter. Inparticular, we described the synthesis of model compounds and the difficulties encountered duringthe transition to porphyrin derivatives. However, in view of results obtained and opportuni…
“Two-Story” Calix[6]arene-Based Zinc and Copper Complexes: Structure, Properties, and O 2 Binding
2017
International audience; A new “two-story” calix[6]arene-based ligand was synthesized, and its coordination chemistry was explored. It presents a tren cap connected to the calixarene small rim through three amido spacers. X-ray diffraction studies of its metal complexes revealed a six-coordinate ZnII complex with all of the carbonyl groups of the amido arms bound and a five-coordinate CuII complex with only one amido arm bound. These dicationic complexes were poorly responsive toward exogenous neutral donors, but the amido arms were readily displaced by small anions or deprotonated with a base to give the corresponding monocationic complexes. Cyclic voltammetry in various solvents showed a r…
Charge-transfer driven by ultrafast spin-transition in a CoFe Prussian blue analogue
2020
Photoinduced charge-transfer is an important process in nature and technology and is responsible for the emergence of exotic functionalities, such as magnetic order for cyanide-bridged bimetallic coordination networks. Despite its broad interest and intensive developments in chemistry and material sciences, the atomic-scale description of the initial photoinduced process, which couples intermetallic charge-transfer and spin transition, has been debated for decades; it has been beyond reach due to its extreme speed. Here we study this process in a prototype cyanide-bridged CoFe system by femtosecond X-ray and optical absorption spectroscopies, enabling the disentanglement of ultrafast electr…
Coordination Chemistry of a Bis(Tetrazine) Tweezer: A Case of Host-Guest Behavior with Silver Salts
2021
The carbon-carbon cross-coupling of phenyl s-tetrazine (Tz) units at their ortho-phenyl positions allows the formation of constrained bis(tetrazines) with original tweezer structures. In these compounds, the face-to-face positioning of the central tetrazine cores is reinforced by π-stacking of the electron-poor nitrogen-containing heteroaromatic moieties. The resulting tetra-aromatic structure can be used as a weak coordinating ligand with cationic silver. This coordination generates a set of bis(tetrazine)-silver(I) coordination complexes tolerating a large variety of counter anions of various geometries, namely, PF6−, BF4−, SbF6−, ClO4−, NTf2−, and OTf−. These compounds were characterized…
New Microbe Killers : Self-Assembled Silver(I) Coordination Polymers Driven by a Cagelike Aminophosphine
2019
New Ag(I) coordination polymers, formulated as [Ag(μ-PTAH)(NO3)2]n (1) and [Ag(μ-PTA)(NO2)]n (2), were self-assembled as light- and air-stable microcrystalline solids and fully characterized by NMR and IR spectroscopy, electrospray ionization mass spectrometry (ESI-MS(±), elemental analysis, powder (PXRD) and single-crystal X-ray diffraction. Their crystal structures reveal resembling 1D metal-ligand chains that are driven by the 1,3,5-triaza-7-phospaadamantane (PTA) linkers and supported by terminal nitrate or nitrite ligands; these chains were classified within a 2C1 topological type. Additionally, the structure of 1 features a 1D!2D network extension through intermolecular hydrogen bonds…
Multiproperty complexes of 4d and 4f metal ions based on biomolecules: from fundamental research to potential applications
2023
El trabajo desarrollado en esta Tesis se enmarca en el campo de la Química de Coordinación y el Magnetismo Molecular, vectores base para el desarrollo de múltiples aplicaciones en Nanomedicina y Nanotecnología. El estudio de los compuestos de coordinación tiene una larga historia que se remonta a principios del siglo XIX, con notables contribuciones de químicos como Berzelius y Jørgensen. Esta rama de la química se centra en la comprensión de las propiedades de unión de los ligandos (moléculas o aniones donadores de electrones) a los iones metálicos. Las teorías de Alfred Werner sobre la coordinación de iones metálicos a principios del siglo XX marcaron un hito importante en este campo. El …
Bioinorganic Chemistry Chapter 1
2018
Tema 1 de la part de Bioinorgànica de l'assignatura Química Inorgànica Avançada Chapter 1 of the Bioinorganic part of the course on Advanced Inorganic Chemistry
A general diastereoselective synthesis of highly functionalized ferrocenyl ambiphiles enabled on a large scale by electrochemical purification
2017
International audience; A general synthesis of highly functionalized ferrocenes, which include (P,B)- and (N,B)-ambiphiles, has been developed at a multigram scale. Diastereoselective stepwise modification of di-tert-butylated ferrocenes included the unprecedented separation of electroactive species. Bulky alkyl groups on ferrocenes ensure planar chirality of ambiphiles and enforce closer proximity of antagonist Lewis functions.
A robust nanoporous supramolecular metal–organic framework based on ionic hydrogen bonds
2014
International audience; Hydrogen-bond assembly of tripod-like organic cations [H3-MeTrip]3+ (1,2,3-tri(4′-pyridinium-oxyl)-2-methylpropane) and the hexa-anionic complex [Zr2(oxalate)7]6− leads to a structurally, thermally, and chemically robust porous 3D supramolecular framework showing channels of 1 nm in width. Permanent porosity has been ascertained by analyzing the material at the single-crystal level during a sorption cycle. The framework crystal structure was found to remain the same for the native compound, its activated phase, and after guest resorption. The channels exhibit affinities for polar organic molecules ranging from simple alcohols to aniline. Halogenated molecules and I2 …
Theoretical Studies of the Reactivity of Cyclopentadienyl Nitrosyl Alkyl Species of Molybdenum and Tungsten
2000
International audience; The reactivity differences observed experimentally for Cp*W(NO)(CH2CMe3)2 and CpMo(NO)(CH2CMe3)2 have been investigated using density functional theory (DFT) techniques. The reactions of the CpW(NO)(CH2) model complex with NH3 and CH4 are more exothermic and have lower activation barriers than the corresponding processes for CpMo(NO)(CH2). The η2(C,H) methane complex CpM(NO)(CH2)(CH4) (M = Mo, W) can undergo two competitive processes: C−H activation to afford CpM(NO)(CH3)2 or loss of methane. The relative barrier heights are almost identical for M = W, whereas the formation of CpM(NO)(CH3)2 is significantly disfavored for M = Mo. The activation of C−H and N−H bonds …