Self-Assembled M2L4 Nanocapsules: Synthesis, Structure and Host-Guest Recognition Toward Square Planar Metal Complexes

Metallosupramolecular cages of the general formulas [M2(L)4][X]4 can be self-assembled in good yields, where M = Pd, X = NO3, L = L1 (1a); M = Pd, X = OTf, L = L1 (1b); M = Pt, X = OTf, L = L1 (2); M = Pd, X = OTf, L = L2 (3); L1 = 1,3-bis(pyridin-3-ylethynyl)-5-methoxybenzene; and L2 = 2,6-(pyridin-3-ylethynyl)- 4-methoxyaniline, respectively. These cages have been fully characterized using 1H, 13C NMR, elemental analysis, IR spectroscopy, and electrospray mass spectrometry. Additionally the molecular structure of [Pd2(L1)4][OTf]4 (1b) was confirmed using single crystal X-ray diffraction. The capacity of central cavities of M2L4 cages to accommodate square planar metal complexes was investigated. In particular, the tetracationic cage [Pd2(L2)4][OTf]4 (3) was found to encapsulate the anionic metal complex [PtCl4]2− through electrostatic interactions and also via hydrogen bonding with the amino groups of the bridging ligand displayed by this nanocage

Synthèse d'aryl et de polyarylamines par catalyse au nickel pour le développement de nouveaux matériaux conducteurs

Les travaux de cette thèse décrivent la mise au point de nouveaux catalyseurs de nickel pour la réaction d'arylamination ainsi que la caractérisation physicochimique des (poly)arylamines préparées. Dans une première partie, le catalyseur Ni(0)/bpy a été utilisé pour la synthèse de di- et de triaminobenzènes à partir de chlorures d'aryle. Parmi les nouveaux composés préparés, les 1,3,5-tris[4-aminophényl]benzènes ont montré un comportement électrochimique très original et la formation de complexes de transfert de charge a été mise en évidence au cours de leur oxydation. La seconde partie du mémoire décrit le développement d'un nouveau catalyseur au nickel ligandé par un carbène N-hétérocyclique, SIPr. De champ d'application nettement plus large que le catalyseur Ni(0)/bpy, il permet l'arylation efficace de toutes les classes d'amines. La synthèse, à l'aide du catalyseur Ni(0)/SIPr, de nouvelles naphthidines, oxydables en di(radicaux cations) stables, est finalement décrite.This work describes the preparation of new nickel catalysts for C-N cross coupling reactions and the physicochemical caracterisation of new polyarylamines synthetised. In a first part, the Ni(0)/bpy catalyst was used for the synthesis of di- and triaminobenzenes from aryl chlorides. Among products prepared, 1,3,5-tris[4-aminophenyl]benzenes showed a original electrochemical behaviour and the formation by oxidation of charge transfert complexes was demonstrated. In the second part, the development of a new nickel catalyst, noted Ni(0)/SIPr in which nickel is coordinated by a N-heterocyclic carbene is described. Contrary to the Ni(0)/bpy catalyst, the Ni(0)/SIPr reagent is efficient for the arylation of all classes of amines. The synthesis of new naphthidines using the Ni(0)/SIPr catalyst, and their oxidation into stable di(radical cation) is finally reported.NANCY1-SCD Sciences & Techniques (545782101) / SudocSudocFranceF

Design, Self-Assembly, and Molecular Structures of 3D Copper(II) Capsules Templated by BF4- Guest Anions

International audienceThe synthesis of two 3D M2L4 copper(II) capsules, [BF4⊂(CH3CN)2Cu2(L1)4][BF4]3 (1) and [BF4⊂(BF4)2Cu2(L1)4][BF4] (2), by using 1,3-(benzimidazol-1-ylmethyl)-2,5-dimethoxy-4,6-dimethylbenzene (L1) as a semirigid exobidentate ligand and [Cu(CH3CN)4][BF4]2 as a metallobrick is reported. Single-crystal X-ray diffraction studies show the encapsulation of a BF4- anion in 1 and 2. Moreover, 2 displayed three coordinated BF4- anions, which is rare in supramolecular coordination host-guest chemistry. Remarkably, in both metallocages the weakly coordinated BF4- anion acts as a template and interacts with the metal center through a weak Cu···F contact. (\textcopyright Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009

Self-Assembled M 2 L 4 Nanocapsules: Synthesis, Structure and Host-Guest Recognition Toward Square Planar Metal Complexes

International audienceMetallosupramolecular cages of the general formulas [M 2 (L) 4 ][X] 4 can be self-assembled in good yields, where M = Pd, X = NO 3 , L = L 1 (1a); M = Pd, X = OTf, L = L 1 (1b); M = Pt, X = OTf, L = L 1 (2); M = Pd, X = OTf, L = L 2 (3); L 1 = 1,3-bis(pyridin-3-ylethynyl)-5-methoxybenzene; and L 2 = 2,6-(pyridin-3-ylethynyl)-4-methoxyaniline, respectively. These cages have been fully characterized using 1 H, 13 C NMR, elemental analysis, IR spectroscopy, and electrospray mass spectrometry. Additionally the molecular structure of [Pd 2 (L 1) 4 ][OTf] 4 (1b) was confirmed using single crystal X-ray diffraction. The capacity of central cavities of M 2 L 4 cages to accommodate square planar metal complexes was investigated. In particular, the tetracationic cage [Pd 2 (L 2) 4 ][OTf] 4 (3) was found to encapsulate the anionic metal complex [PtCl 4 ] 2− through electrostatic interactions and also via hydrogen bonding with the amino groups of the bridging ligand displayed by this nanocage

Naphthidine di(radical cation)s-stabilized palladium nanoparticles for efficient catalytic Suzuki–Miyaura cross-coupling reactions

International audienceStable Pd(0) nanoparticles were prepared at room temperature in 1,4-dioxane from PdCl2 using N,N′-bis(4-methoxyphenyl)-(1,1′-binaphthyl)-4,4′-diamine (naphthidine) as reducing and stabilizing agent. This procedure resulted in Pd(0) particles possessing an average diameter of ca. 25nm stabilized against aggregation due to a barrier of the naphthidine di(radical cation) Napht2.2+. These particles were evaluated for their capability to act as catalysts in Suzuki–Miyaura coupling reactions. The Pd(0)/Napht2.2+ provides a general and convenient method to prepare biaryls from aryl bromides or iodides and boronic acids with a broad range of functional groups in 1,4-dioxane at 80°C and under aerobic conditions

Hierarchical Self-Assembly of Polyoxometalate-Based Organo Palladium(II) Metallomacrocycles via Electrostatic Interactions

International audienceThe design and synthesis of a supramolecular square composed of polyoxometalate-based hybrid donors and ethylenediamine palladium(II) nodes are reported. The structure of the metallomacrocycle scaffold was inferred by diffusion NMR, small-angle X-ray scattering (SAXS), and molecular modeling. The metallomacrocycle scaffold that contains negatively and positively charged subunits can further self-assemble owing to a competition between the solvation energy of the discrete species and intermolecular electrostatic interactions. When the dissociating character of the solvent was lowered or when in the presence of a protic solvent, different types of multiscale organizations (vesicles and pseudo-1D structures) were selectively formed and were characterized by SAXS and transmission electron microscopy

Copper octacarboxyphthalocyanine as sensitizer of graphitic carbon nitride for efficient dye degradation under visible light irradiation

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