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2023



  • 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, janv. 2023.
    Résumé : 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.
    Mots-clés : ARC.
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2022



  • A. Groué, J. - P. Tranchier, G. Gontard, M. Jean, N. Vanthuyne, et 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, mars 2022.
    Résumé : 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.
    Mots-clés : ARC, chiral resolution, circular dichroism, configurational stability, enantiopure.
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2021



  • G. Basuyaux, A. Amar, C. Troufflard, A. Boucekkine, R. Métivier, M. Raynal, J. Moussa, L. Bouteiller, et 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, sept. 2021.
    Résumé : 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.
    Mots-clés : Aggregation, ARC, Bisurea, Competitor, Luminescence, POLYMERES, Pt⋅⋅⋅Pt interactions, Sergeants-and-soldiers.
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2020



  • R. El-Hnayn, L. Canabady-Rochelle, C. Desmarets, L. Balan, H. Rinnert, O. Joubert, G. Medjahdi, H. Ben Ouada, et 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, janv. 2020.
    Résumé : 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.
    Mots-clés : 2, 2’-(ethylenedioxy)bis(ethylamine), ARC, graphene quantum dots, optical properties, POLE 1, redox-active nanoparticles.
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  • A. Li, Y. Li, L. - M. Chamoreau, C. Desmarets, L. Lisnard, et 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.
    Résumé : 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.
    Mots-clés : ARC, ERMMES, POLE 1, POLE 2.
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2018



  • S. ben Moussa, A. Mehri, M. Gruselle, P. Beaunier, G. Costentin, et 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, juin 2018.
    Résumé : 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.
    Mots-clés : Apatite surface, ARC, Glutamic acid, Hybrid compound, Hydrothermal method, POLE 1.
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2023
1. Luminescent complexes of platinum, iridium, and coinage metals containing N‑heterocyclic carbene ligands : Design, structural diversity, and photophysical properties.
H. Amouri
Chemical Reviews., 2023, vol, 123, no 01, p 230-270.
https://doi.org/10.1021/acs.chemrev.2c00206

2022

1. Rational design of mono- and bi-nuclear cyclometalated Ir(III) complexes containing di-pyridylamine motifs : Synthesis, structure and luminescent properties.
H. Sesolis, G. Gontard, M. N. Rager, E. Bandini, A. S. Moncada, A. Barbieri and H. Amouri
Molecules, 2022, vol 27, no 17, p 6003.
https://doi.org/10.3390/molecules27186003

2. Apatites based catalysts : A tentative classification
M. Gruselle, K. Tonsuaadu, P. Gredin and C. Len
Mol. Catal., 2022, vol 519, no 8, p 112146.
https://doi.org/10.1016/j.mcat.2022.112146

3. Cyclometallated Rhodium and Iridium Complexes Containing Masked Catecholates : Synthesis, Structure, Electrochemistry and Luminescent Properties.
A. Groue, J.-P. Tranchier, M. N. Rager, G. Gontard, R. Metivier, O. Buriez, A. Khatyr, M. Knorr and H. Amouri
Inorg. Chem., 2022, vol 61, no12, p 4909-4918.
https://doi.org/10.1021/acs.inorgchem.1c03656

4. Enantiopure cyclometalated Rh(III) and Ir(III) complexes displaying rigid configuration at metal center : Design, structures, chiroptical properties and role of the iodide ligand.
A. Groue, J.-P. Tranchier, G. Gontard, M. Jean, N. Vanthuyne and H. Amouri
Chemistry, 2022, vol 4, no 1, p 156.
https://doi.org/10.3390/chemistry4010014

5. Enantiopure, Luminescent, Cyclometalated Ir(III) Complexes with N-Heterocyclic Carbene-Naphthalimide Chromophore : Design, Vibrational Circular Dichroism and TD-DFT Calculations.
A. Groue, E. Montier-Sorkine, Y. Cheng, M. N. Rager, M. Jean, N. Vanthuyne, J. Crassous, A. C. Lopez, A. S. Moncada, A. Barbieri, A. L. Cooksy and H. Amouri
Dalton Trans., 2022, vol 51, no 7, p 2750-2759.
https://doi.org/10.1039/D1DT04006E

2021
1. Optically Active Pt-terpyridyl Coordination Assemblies Derived from Planar Chiral Metallothioligands.
E. Puig, G. Gontard, M. N. Rager and H. Amouri
Inorg. Chim. Acta., 2021, vol 517, p 120208.
https://doi.org/10.1016/j.ica.2020.120208

2. Cyclometallated Pt(II) Complexes Containing a Functionalized Bis-Urea Alkynyl Ligand : Probing Aggregation Mediated by Hydrogen Bonds versus Pt∙∙∙Pt and π-π Interactions.
G. Basuyaux, A. Amar, C. Troufflard, A. Boucekkine, R. Metivier, M. Raynal, J. Moussa, L. Bouteiller and H. Amouri
Eur. J. Inorg. Chem., 2021, no 35, p 3622-3631.
https://doi.org/10.1002/ejic.202100499

2020
1. Hierarchical Self-Assembly of Polyoxometalate-Based Organo Palladium(II) Metallomacrocycles via Electrostatic Interactions
R. Salles, B. Abecassis, E. Derat, D. Brouri, A. Bernard, Q. Zhang, A. Proust, C. Desmarets and G. Izzet
Inorg. Chem., 2020, vol 59, no 4, p 2458-2463.
https://doi.org/10.1021/acs.inorgchem.9b03333

2. A Bis-Polydentate Oxamate-Based Achiral Ligand That Can Stabilize a Macrocyclic Mixed Valence Compound or Induce a 1D Helical Chain
A. Li, Y. Li, L.-M. Chamoreau, C. Desmarets, L. Lisnard and Y. Journaux
Eur. J. Inorg. Chem., 2020, no 34, p 3311-3319.
https://doi.org/10.1002/ejic.202000490

3. Synthesis of novel photoluminescent pyridinium-betaine-type molecules
A. Hassoun, A. Benchohra, O. Khaled, D. Seghouane and J. Moussa
Monatsh. fur Chem., 2020, vol 151, p 799-806.
https://doi.org/10.1007/s00706-020-02591-9

2019
1. Capturing a Square Planar Gold(III) Complex Inside a Platinum Nanocage : A Combined Experimental and Theoretical Study.
E. Puig, C. Desmarets, G. Gontard, M. N. Rager, A. L. Cooksy and H. Amouri
Inorg. Chem., 2019, vol 58, no 5, p 3189-3195.
https://doi.org/10.1021/acs.inorgchem.8b03272

2. Appealing copper (I) and silver (I) coordination polymers with an unprecedented betainoid assembling ligand.
D. Amelot, A. Hassoun, L. M. Chamoreau, H. Amouri, J. Moussa
Edelweiss Chem. Sci. J., 2019, vol 1, no 1, p24-28.
https://doi.org/10.33805/2641-7383.106

3. Unique Class of enantiopure N-heterocyclic carbene half-sandwich Ir(III) complexes with stable configurations : Probing five-membered versus six-membered iridacycles.
A. Groue, J.-P. Tranchier, M.-N. Rager, G. Gontard, M. Jean, N. Vanthuyne, H. R. Pearce, A. L. Cooksy and H. Amouri
Inorg. Chem., 2019, vol 58, no5, p2930-2933.
https://doi.org/10.1021/acs.inorgchem.8b03469

4. Extra hydrogen-bonding interactions by peripheral indole groups stabilizes benzene 1,3,5-tricarboxamide helical assemblies.
G. Basuyaux, A. Desmarchelier, G. Gontard, N. Vanthuyne, J. Moussa, H. Amouri, M. Raynal and L. Bouteiller
Chem. Commun., 2019, vol 55, no 59, p 8548-8551.
https://doi.org/10.1039/C9CC03906F

2018

1. Dependence of the interaction mechanisms between L-serine and O-phospho-L-serine with calcium hydroxyapatite and copper modified hydroxyapatite in relation with the acidity of aqueous medium
K. Tonsuaadu, M. Gruselle, F. Kriisa, A. Trikkel, P. Gredin and D. Villemin
J. Biol. Inorg. Chem., 2018, vol 23, p929-937.
https://doi.org/10.1007/s00775-018-1594-0

2. Convenient approach to luminescent cyclometalated platinum(II) complexes with organometallic -bonded Benzenedithiolate.
H. Sesolis, G. Gontard, A. Jutand, M. P. Gullo, E. Bandini, A. Barbieri and H. Amouri
Eur. J. Inorg. Chem., 2018, no 34, p 3804-3812.
https://doi.org/10.1002/ejic.201800561

3. Cyclometalated N-heterocyclic carbene iridium(III) complexes with naphthalimide chromophores : A novel class of phosphorescent heteroleptic compounds.
P.-H. Lanoe, J. Chan, A. Groue, G. Gontard, A. Jutand, M.-N. Rager, N. Armaroli, F. Monti, A. Barbieri and H. Amouri
Dalton Trans., 2018, vol 47, no 10, p 3440-3451.
https://doi.org/10.1039/C7DT04369D

4. Combined effect of magnesium and amino glutamic acid on the structure of hydroxyapatite prepared by hydrothermal method.
S. ben Moussa, A. Mehri, M. Gruselle, P. Beaunier, G. Costentin and B. Badraoui
Mater. Chem. Phys., 2018, vol 212, p 21-29.
https://doi.org/10.1016/j.matchemphys.2018.03.017

2017

1. Chiral two bladed ML2 metallamacrocycles : Design, structures and solution behavior.
H. Soudry, C. Desmarets, G. Gontard, T. Edgington, A. L. Cooksy and H. Amouri
Dalton Trans., 2017, vol 46, no 31, p10240-10245.
https://doi.org/10.1039/C7DT01151B

2. Dinuclear (N^C^N) Pincer Pt(II) Complexes with Bridged Organometallic Linkers : Synthesis, Structures, Self-Aggregation and Photophysical Properties
H. Sesolis, C. K.-M. Chan, G. Gontard, H. L.-K. Fu, V. W.-W. Yam and H. Amouri
Organometallics, 2017, vol 36, no 24, p 4794-4801.
https://doi.org/10.1021/acs.organomet.7b00680

3. Hybrid organic-inorganic materials based on hydroxyapatite structure
S. B. Moussa, H. Bachoua, M. Gruselle, P. Beaunier, A. Flambard and B. Badraoui,
J. Solid. State Chem., 2017, vol 248, p171-177.
https://doi.org/10.1016/j.jssc.2017.02.004

4. Luminescent cyclometalated platinum(II) complexes with p-bonded catecholate organometallic ligands
J. Moussa, A. Loch, L.-M. Chamoreau, A. D. Esposti, E. Bandini, A. Barbieri and H. Amouri,
Inorg. Chem., 2017, vol 56, no 4, p2050-2059.
https://doi.org/10.1021/acs.inorgchem.6b02731

5. N-Heterocyclic carbene coinage metal complexes containing naphthalimide chromophore : Design, structure and photophysical properties
P.-H. Lanoe, B. Najjari, F. Hallez, G. Gontard and H. Amouri
Inorganics, 2017, vol 5, no 3, p58.
https://doi.org/10.3390/inorganics5030058

6. Tunable Calcium-Apatites as Solid Catalysts for Classical Organic Reactions
M. Gruselle and K. Tonsuaadu
Curr. Org. Chem., 2017, vol 21, no 8, p 688-697.
https://doi.org/10.2174/1385272821666161219155302