A soluble cyanide-bridged {Fe 4 Ni 4 } box encapsulating a Cs + ion: synthesis, structure and electronic properties
| Autor: | Amina Benchohra, Yanling Li, Jessica L. Tami, Omar Khaled, Rodrigue Lescouëzec, Rémi Plamont, Juan-Ramón Jiménez, Geoffrey Gontard |
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| Přispěvatelé: | Institut Parisien de Chimie Moléculaire (IPCM), Chimie Moléculaire de Paris Centre (FR 2769), Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS) |
| Jazyk: | angličtina |
| Rok vydání: | 2018 |
| Předmět: |
010405 organic chemistry
Cyanide electronic communication chemistry.chemical_element Nuclear magnetic resonance spectroscopy caesium molecular cage 010402 general chemistry 01 natural sciences 0104 chemical sciences Ion Supramolecular assembly Crystallography Paramagnetism chemistry.chemical_compound chemistry Caesium Materials Chemistry Proton NMR [CHIM]Chemical Sciences cyanide ligand Physical and Theoretical Chemistry Cyclic voltammetry |
| Zdroj: | Journal of Coordination Chemistry Journal of Coordination Chemistry, Taylor & Francis, 2018, 71 (5), pp.601-614. ⟨10.1080/00958972.2018.1442575⟩ |
| ISSN: | 0095-8972 |
| DOI: | 10.1080/00958972.2018.1442575⟩ |
| Popis: | Cyanide coordination clusters have received attention for their electronic and magnetic properties. Here, we synthesized a new octametallic cyanide box encapsulating a Cs+. The cationic complex Cs⊂[FeIII4(Tp)4NiII4(NMe2Tp)4(μ-CN)12]+ was crystallized as a BF4− salt and its structure reveals that the cesium ion interacts with the twelve cyanide edges. These interactions are likely responsible for the remarkable stability of the supramolecular assembly, which maintains its integrity in solution, as shown by NMR spectroscopy, mass spectrometry, and cyclic voltammetry experiments. The 1H NMR spectrum of 1 shows well-resolved signals, which are strongly shifted due to the paramagnetic nature of the cage. The encapsulated caesium ion is also affected by the paramagnetic cage and shows a strongly shifted 133Cs paramagnetic NMR signal. The {Fe4Ni4} box shows remarkable redox flexibility with five accessible oxidation states, which correspond to the reversible oxidation/reduction of the four FeIII/FeII ions. The separation of the four consecutive redox waves accounts for the occurrence of an efficient electronic communication between the metal ions through the cyanide bridges. The cyanide bridges are also efficient in transmitting a ferromagnetic interaction between the iron and nickel ions as shown by the magnetic properties. |
| Databáze: | OpenAIRE |
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