916902-57-3Relevant academic research and scientific papers
Divergent Synthesis of Molecular Winch Prototypes
Gisbert, Yohan,Abid, Seifallah,Kammerer, Claire,Rapenne, Gwéna?l
, p. 16242 - 16249 (2021/10/16)
We report the synthesis of conceptually new prototypes of molecular winches with the ultimate aim to investigate the work performed by a single ruthenium-based molecular motor anchored on a surface by probing its ability to pull a load upon electrically-driven directional rotation. According to a technomimetic design, the motor was embedded in a winch structure, with a long flexible polyethylene glycol chain terminated by an azide hook to connect a variety of molecular loads. The structure of the motor was first derivatized by means of two sequential cross-coupling reactions involving a penta(4-halogenophenyl)cyclopentadienyl hydrotris(indazolyl)borate ruthenium(II) precursor and the resulting benzylamine derivative was next exploited as key intermediate in the divergent synthesis of a family of nanowinch prototypes. A one-pot method involving sequential peptide coupling and Cu-catalyzed azide-alkyne cycloaddition was developed to yield four loaded nanowinches, with load fragments encompassing triptycene, fullerene and porphyrin moieties.
Expedient Synthesis of Thioether-Functionalized Hydrotris(indazolyl)borate as an Anchoring Platform for Rotary Molecular Machines
Erbland, Guillaume,Gisbert, Yohan,Rapenne, Gwéna?l,Kammerer, Claire
, p. 4731 - 4739 (2018/09/14)
Major improvements in the synthesis of surface-mounted rotary molecular machines based on ruthenium(II) complexes are reported. The development of a one-pot indium(III)-mediated “N-deprotection/ester reductive sulfidation” sequence allowed step economy, reproducibility and high efficiency in the synthesis of the thioether-functionalized tripodal ligand. Switching to the thallium salt of hydrotris(indazolyl)borate and to microwave heating further optimized the preparation of the common intermediate in the modular synthesis of symmetric and dissymmetric molecular motors and gears. The penta(4-bromophenyl)cyclopentadienyl ruthenium(II) key precursor is now reproducibly synthesized in 5 steps and 31 % overall yield on the longest linear sequence. Subsequent fivefold Suzuki–Miyaura coupling with ferroceneboronic acid led to a new C5-symmetric pentaferrocenyl molecular motor.
Synthesis of new tripodal tri-functionalized hydrotris(indazol-1-yl)borate ligands and x-ray structures of their cyclopentadieneruthenium complexes
Carella, Alexandre,Vives, Guillaume,Cox, Tara,Jaud, Jo?l,Rapenne, Gwéna?l,Launay, Jean-Pierre
, p. 980 - 987 (2007/10/03)
Two new tripodal ligands designed to anchor complexes onto surfaces have been synthesized. They integrate ester or thioether functions at the 6-position of the indazoles. Potassium hydrotris[6-(ethoxycarbonyl)indazolyl]borate and potassium hydrotris{6-[(ethylsulfanyl)methyl]indazolyl}borate exhibit three pendant groups oriented to anchor complexes onto an oxide and a metallic surface, respectively. Their complexation with [RuCp(CH3CN) 3]PF6 yielded two piano-stool-shaped complexes that were characterized by X-ray diffraction. Comparison with the synthesized unfunctionalized analog showed that the three 6-substituted functions do not interfere with the coordination site and are particularly well oriented for surface deposition. Wiley-VCH Verlag GmbH & Co. KGaA, 2006.
