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  • H. Amouri, “Luminescent Complexes of Platinum, Iridium, and Coinage Metals Containing N-Heterocyclic Carbene Ligands: Design, Structural Diversity, and Photophysical Properties”, Chemical Reviews, vol. 123, no. 1, p. 230-270, Jan. 2023.
    Abstract: The employment of N-heterocyclic carbenes (NHCs) to design luminescent metal compounds has been the focus of recent intense investigations because of the strong σ-donor properties, which bring stability to the whole system and tend to push the d–d dark states so high in energy that they are rendered thermally inaccessible, thereby generating highly emissive complexes for useful applications such as organic light-emitting diodes (OLEDs), or featuring chiroptical properties, a field that is still in its infancy. Among the NHC complexes, those containing organic chromophores such as naphthalimide, pyrene, and carbazole exhibit rich emission behavior and thus have attracted extensive interest in the past five years, especially carbene coinage metal complexes with carbazolate ligands. In this review, the design strategies of NHC-based luminescent platinum and iridium complexes with large spin–orbit-coupling (SOC) are described first. Subsequent paragraphs illustrate the recent advances of luminescent coinage metal complexes with nucleophilic- and electrophilic-based carbenes based on silver, gold, and copper metal complexes that have the ability to display rich excited state emissions in particular via thermally activated delayed fluorescence (TADF). The luminescence mechanism and excited state dynamics are also described. We then summarize the advance of NHC–metal complexes in the aforementioned fields in recent years. Finally, we propose the development trend of this fast-growing field of luminescent NHC–metal complexes.
    Tags: ARC.


  • A. Groué, J. - P. Tranchier, G. Gontard, M. Jean, N. Vanthuyne, and H. Amouri, “Enantiopure Cyclometalated Rh(III) and Ir(III) Complexes Displaying Rigid Configuration at Metal Center: Design, Structures, Chiroptical Properties and Role of the Iodide Ligand”, Chemistry, vol. 4, no. 1, p. 156-167, Mar. 2022.
    Abstract: Enantiopure N-heterocyclic carbene half-sandwich metal complexes of the general formula [Cp*M(C^C:)I] (M = Rh, Ir; C^C: = NI-NHC; NI-H = Naphthalimide; NHC = N-heterocyclic carbene) are reported. The rhodium compound was obtained as a single isomer displaying six membered metallacycle and was resolved on chiral column chromatography to the corresponding enantiomers (S)-[Cp*Rh(C^C:)I] (S)-2 and (R)-[Cp*Rh(C^C:)I] (R)-2. The iridium congener, however, furnishes a pair of regioisomers, which were resolved into (S)-[Cp*Ir(C^C:)I] (S)-3 and (R)-[Cp*Ir(C^C:)I] (R)-3 and (S)-[Cp*Ir(C^C:)I] (S)-4 and (R)-[Cp*Ir(C^C:)I] (R)-4. These regioisomers differ from each other, only by the size of the metallacycle; five-membered for 3 and six-membered for 4. The molecular structures of (S)-2 and (S)-4 are reported. Moreover, the chiroptical properties of these compounds are presented and discussed. These compounds display exceptional stable configurations at the metal center in solution with enantiomerization barrier ΔG≠ up to 124 kJ/mol. This is because the nature of the naphthalimide-NHC clamp ligand and the iodide ligand contribute to their configuration’s robustness. In contrast to related complexes reported in the literature, which are often labile in solution.
    Tags: ARC, chiral resolution, circular dichroism, configurational stability, enantiopure.


  • G. Basuyaux, A. Amar, C. Troufflard, A. Boucekkine, R. Métivier, M. Raynal, J. Moussa, L. Bouteiller, and H. Amouri, “Cyclometallated Pt(II) Complexes Containing a Functionalized Bis-Urea Alkynyl Ligand: Probing Aggregation Mediated by Hydrogen Bonds versus Pt⋅⋅⋅Pt and π−π Interactions”, European Journal of Inorganic Chemistry, vol. 2021, no. 35, p. 3622-3631, Sep. 2021.
    Abstract: Abstract Neutral cyclometallated Pt(II) complexes [(C^Nt?Bu^Nt?Bu)Pt?R] (4?5) containing a bis-urea alkynyl (R) ligand have been prepared and fully characterized. The dichotomous nature of 4?5 makes it difficult to anticipate which interactions (hydrogen bonds, π?π stacking and Pt???Pt) will dominate their assembly process. The aggregation properties of 4?5 were thus probed by multifarious analytical (UV/Vis, FT-IR, NMR, MS, CD, emission) and computational (DFT, TD-DFT) techniques. CD analyses of sergeants-and-soldiers type mixtures between 4 and an enantiopure Pt-free monomer (S,S)-3 reveal that no amplification of supramolecular helicity occurs in this system. In fact, complex 4 acts as competitor or chain capper, likely through hydrogen bonding, of the homochiral assemblies formed by (S,S)-3. In DMSO, 1H NMR and DOSY analyses indicate that 4 and 5 form aggregates. Likewise, the aggregation is promoted by the addition of H2O as suggested by red shift of the lowest energy emission band, which might originate from a 3MMLCT excited state. TD-DFT calculations confirm that self-aggregation occurs through Pt???Pt and π?π interactions yielding head-to-tail aggregates in DMSO and DMSO/H2O mixtures. Our study therefore suggests a (condition dependent) competitive rather than a cooperative mode of action of the different types of interactions present in aggregates of 4?5.
    Tags: Aggregation, ARC, Bisurea, Competitor, Luminescence, POLYMERES, Pt⋅⋅⋅Pt interactions, Sergeants-and-soldiers.


  • R. El-Hnayn, L. Canabady-Rochelle, C. Desmarets, L. Balan, H. Rinnert, O. Joubert, G. Medjahdi, H. Ben Ouada, and R. Schneider, “One-Step Synthesis of Diamine-Functionalized Graphene Quantum Dots from Graphene Oxide and Their Chelating and Antioxidant Activities”, Nanomaterials, vol. 10, no. 1, p. 104, Jan. 2020.
    Abstract: 2,2’-(Ethylenedioxy)bis(ethylamine)-functionalized graphene quantum dots (GQDs) were prepared under mild conditions from graphene oxide (GO) via oxidative fragmentation. The as-prepared GQDs have an average diameter of ca. 4 nm, possess good colloidal stability, and emit strong green-yellow light with a photoluminescence (PL) quantum yield of 22% upon excitation at 375 nm. We also demonstrated that the GQDs exhibit high photostability and the PL intensity is poorly affected while tuning the pH from 1 to 8. Finally, GQDs can be used to chelate Fe(II) and Cu(II) cations, scavenge radicals, and reduce Fe(III) into Fe(II). These chelating and reducing properties that associate to the low cytotoxicity of GQDs show that these nanoparticles are of high interest as antioxidants for health applications.
    Tags: 2, 2’-(ethylenedioxy)bis(ethylamine), ARC, graphene quantum dots, optical properties, POLE 1, redox-active nanoparticles.

  • A. Li, Y. Li, L. - M. Chamoreau, C. Desmarets, L. Lisnard, and Y. Journaux, “A Bis-Polydentate Oxamate-Based Achiral Ligand That Can Stabilize a Macrocyclic Mixed Valence Compound or Induce a 1D Helical Chain”, European Journal of Inorganic Chemistry, vol. 2020, no. 34, p. 3311-3319, 2020.
    Abstract: The reaction of the N-(2-hydroxyphenyl)oxamate ligand (ohpma) has been investigated with cobalt(II) and copper(II) ions. It has led to two coordination compounds, (TMA)3[CoIII(ohpma)2CoII(MeOH)23]·10H2O·5MeOH (1) and (HNEt3)[Cu(ohpma)] (2). Both compounds have been characterized by single-crystal X-ray diffraction and magnetometry. The X-ray diffraction studies have revealed atypical structures that are not commonly observed in oxamate coordination chemistry with a macrocyclic arrangement for the mixed-valence cobalt-based complex 1, and a helical chiral chain for compound 2. In the latter, the bis-polydentate nature of the (ohpma)3– ligand with distinct tridentate and bidentate coordination sites creates a chirogenic center on the copper ion. The investigation of the magnetic properties shows for complex 1 a single-molecule magnet behavior detectable under static field, while antiferromagnetic interactions dominate the behavior of 2.
    Tags: ARC, ERMMES, POLE 1, POLE 2.


  • S. ben Moussa, A. Mehri, M. Gruselle, P. Beaunier, G. Costentin, and B. Badraoui, “Combined effect of magnesium and amino glutamic acid on the structure of hydroxyapatite prepared by hydrothermal method”, Materials Chemistry and Physics, vol. 212, p. 21-29, Jun. 2018.
    Abstract: Magnesium modified calcium hydroxyapatite of different Mg/Ca compositions have been synthesized using the hydrothermal method in the presence of glutamic acid. The resulting materials have been characterized by X-ray powder diffraction, chemical analysis, IR Spectroscopy and Transmission Electron Microscopy (TEM). X-ray diffraction analysis shows that the resulting materials consist of a single phase having an apatitic structure. IR spectroscopy highlights the presence of carboxylic groups for the organic moieties grafted onto the apatitic surface. The surface properties of apatite samples are determined.
    Tags: Apatite surface, ARC, Glutamic acid, Hybrid compound, Hydrothermal method, POLE 1.
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