Experimental and Theoretical Evidence of π‐d Interactions in Supramolecular Assemblies Based on TTF‐CH=CH‐Py Ligands Tethered to Mo6Xi8 Octahedral Molybdenum Halide Cluster Cores

Prabusankar, Ganesan; Molard, Yann; Cordier, Stéphane; Golhen, Stéphane; Gal, Yann Le; Perrin, Christiane; Ouahab, Lahcène; Kahlal, Samia; Halet, Jean‐François

doi:10.1002/ejic.200900136

Cited by 41 publications

(34 citation statements)

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“…Coronene (C 24 H 12 ; Tokyo Kasei, 98 %) and deuterated coronene (C 24 D 12 ; Cambridge Isotope Laboratories, 97 %) were recrystallized several times from distilled benzene. (TBA) 2 Mo 6 Cl 14 was synthesized according to a modification of a reported method 35…”

Section: Methodsmentioning

confidence: 99%

Isotropic Three‐Dimensional Molecular Conductor Based on the Coronene Radical Cation

et al. 2014

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In this study, we obtained the first cation radical solid of a highly symmetric (D6h) polyaromatic hydrocarbon, coronene, by electrooxidation. The (coronene)3Mo6Cl14 salt, which is formed with an Oh‐symmetric molybdenum cluster unit Mo6Cl142–, has an isotropic cubic structure with Pm$\bar {3}$m symmetry. The presence of two orientations for the coronene molecules related by an in‐plane 90° rotation (merohedral disorder) allows for fourfold symmetry along the <100> direction. The disorder has dynamic features because 2H NMR spectroscopic studies revealed that the coronene molecules undergo an in‐plane flipping motion. The observation of two motional sites with significantly different rotational rates (300 Hz and 5 MHz at 103 K) in an approximate 2:1 ratio appears to be consistent with the splitting of a Raman‐active A1g mode, confirming a random charge‐disproportionated state instead of a uniform partially‐charged state. The slower‐ and faster‐rotating species are assigned to charge‐rich and charge‐poor coronenes, respectively, with respect to C–H···Cl hydrogen bonds with neighboring Mo6Cl142– cluster units. The electrical conductivity of the salt is rather high but is well‐described by a three‐dimensional (3D) variable‐range hopping mechanism, which is possibly associated with the random charge disproportionation. These results provide a significant step forward in developing an isotropic 3D π‐conducting system composed of planar π‐conjugated molecules.

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Section: Methodsmentioning

confidence: 99%

Isotropic Three‐Dimensional Molecular Conductor Based on the Coronene Radical Cation

et al. 2014

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“…These observations have made molybdenum iodide cluster complexes rather attractive for a diverse range of practical applications in biology and medicine (e.g. as photodynamic therapeutic agents, photosensitizers, imaging agents) and analytical chemistry (for detection of trace amounts of molecules which can trigger or quench the luminescence, such as dioxygen or fluoroquinolone antibiotics) , …”

Section: Introductionmentioning

confidence: 99%

Molybdenum Iodides – from Obscurity to Bright Luminescence

Mikhaylov

Sokolov

2019

Eur J Inorg Chem

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This review is dedicated to the chemistry of Mo iodides. These compounds have a humble origin, and for a long time their chemistry has been almost completely neglected. Although important work on mononuclear and dinuclear Mo iodide complexes was done in 1980-1990s, the situation has dramatically changed within the last decade. The finding that the IntroductionThe iodides of transition metals attract much less attention than their chloride and bromide analogues, even though a book dealing exclusively with metal iodides was published half a century ago. [1] This is partly explainable by general lack of current or proposed practical use for this class of compounds. A notable exception offer the volatile iodides of Ti, Zr, and Hf, and of a few other metals, that can be used in the iodide process of van Arkel and de Boer. [2] Among the group 6 metals, this process can be applied for preparation of high purity chromium, which [a] Nikolaev His research interests focus on the coordination chemistry of 4d and 5d transition metals. Maxim Mikhaylov was born in Novosibirsk, (Russia). In 2009-2013 he completed his Ph. D. at the Laboratory of cluster and supramolecular compounds in the Nikolaev Institute of Inorganic Chemistry (NIIC) under suporevision of Prof. Dr. M. N. Sokolov. Now he is a researcher working in the Laboratory of synthesis of cooridnation compounds at NIIC. His research interests include synthesis of novel clusters and cluster complexes for the development of new materials.

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“…[Mo 6 X i 8 X a 6 ] 2− (X = Cl, Br and I) are associated with inorganic or organic cations in many compounds of general formula A 2 [Mo 6 X i 8 X a 6 ] (A = alkali cation, quaternary ammonium, H 3 O + …︁) prepared either by solid state chemistry or by combined use of solid state and solution chemistries. A 2 [Mo 6 X i 8 X a 6 ] series afford thus useful [Mo 6 X i 8 X a 6 ] 2− building blocks with specific physicochemical properties that can be involved in the preparation of molecular assemblies and nanomaterials (e.g., dendrimers, liquid‐crystal and polymer nanocomposites, and functional surfaces) 25–34…”

Section: Photoluminescence Lifetimes Of Zno‐cs2[mo6br14]@sio2 and Cs2mentioning

confidence: 99%

Tunable Visible Emission of Luminescent Hybrid Nanoparticles Incorporating Two Complementary Luminophores: ZnO Nanocrystals and [Mo₆Br₁₄]²⁻ Nanosized Cluster Units

Aubert

Nerambourg

Saito

et al. 2012

Part & Part Syst Charact

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Experimental and Theoretical Evidence of π‐d Interactions in Supramolecular Assemblies Based on TTF‐CH=CH‐Py Ligands Tethered to Mo₆Xⁱ₈ Octahedral Molybdenum Halide Cluster Cores

Abstract: 4+ cluster cores with six redox-active π-conjugated TTF-CH=CH-Py

Cited by 41 publications

References 70 publications

Isotropic Three‐Dimensional Molecular Conductor Based on the Coronene Radical Cation

Isotropic Three‐Dimensional Molecular Conductor Based on the Coronene Radical Cation

Molybdenum Iodides – from Obscurity to Bright Luminescence

Tunable Visible Emission of Luminescent Hybrid Nanoparticles Incorporating Two Complementary Luminophores: ZnO Nanocrystals and [Mo₆Br₁₄]²⁻ Nanosized Cluster Units

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Experimental and Theoretical Evidence of π‐d Interactions in Supramolecular Assemblies Based on TTF‐CH=CH‐Py Ligands Tethered to Mo6Xi8 Octahedral Molybdenum Halide Cluster Cores

Abstract: 4+ cluster cores with six redox-active π-conjugated TTF-CH=CH-Py

Cited by 41 publications

References 70 publications

Isotropic Three‐Dimensional Molecular Conductor Based on the Coronene Radical Cation

Isotropic Three‐Dimensional Molecular Conductor Based on the Coronene Radical Cation

Molybdenum Iodides – from Obscurity to Bright Luminescence

Tunable Visible Emission of Luminescent Hybrid Nanoparticles Incorporating Two Complementary Luminophores: ZnO Nanocrystals and [Mo6Br14]2− Nanosized Cluster Units

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Experimental and Theoretical Evidence of π‐d Interactions in Supramolecular Assemblies Based on TTF‐CH=CH‐Py Ligands Tethered to Mo₆Xⁱ₈ Octahedral Molybdenum Halide Cluster Cores

Tunable Visible Emission of Luminescent Hybrid Nanoparticles Incorporating Two Complementary Luminophores: ZnO Nanocrystals and [Mo₆Br₁₄]²⁻ Nanosized Cluster Units