Frédérique Loiseau

A novel tridentate ligand featuring an acridine core and pyrazole rings, namely 2,7- di-tert-butyl-4,5-di(pyrazol-1-yl)acridine, L, was designed and used to create two ruthenium(II) complexes: [RuL₂](PF₆)₂ and [Ru(tpy)L](PF₆)₂. Surprisingly, the ligand adopted different coordination modes in the complexes: facial coordination for the homoleptic complex and meridional coordination for the heteroleptic complex. The electronic absorption and electrochemical properties were evaluated. Although both complexes exhibited favorable electronic properties for luminescence, neither emitted light at room temperature nor at 77 K. This study highlights the complex interplay between ligand design, coordination mode, and luminescence in ruthenium(II) complexes.

A luminescence study with ab initio calculations that allow us to determine the lowest emitting excited state of a series of neutral Ir(iii) complexes with 2-phenylbenzimidazole cyclometallating ligand.

Cyclometallated iridium(III) and platinum(II) complexes are intensely used in optoelectronics for their photophysical properties and ability to convert excitons from singlet to triplet state, thus improving the device efficiency. In this contribution, we report the multi-steps synthesis of an electrodeficient dipyridylbenzene-like terdentate ligand [N^C^N], namely 2′,6′-dimethyl-2,3′:5′,2″-terpyridine (6), with 18% overall yield. Compound 6 has been employed to synthesize two phosphorescent complexes of platinum(II) and iridium(III), namely compounds 7 and 8, respectively. Both complexes have been characterized by NMR and high resolution mass spectrometry, and demonstrate high luminescence quantum yields in a deaerated solution at room temperature, with 18% and 61% for 7 and 8, respectively. If the iridium(III) complex displays similar emission properties to [Ir(dpyx)(ppy)Cl] (dpyx = 3,5-dimethyl-2,6-dipyridylbenzene and ppy = 2- phenylpyridine), the platinum(II) derivative, with λ_em = 470 nm, is a rare example of a fluorine atom-free blue emitting [N^C^N]PtCl complex.

This work describes the synthesis of a novel zinc(II) porphyrin complex, namely [Meso-4α-tetra-(1,2,3-triazolyl)phenylporphyrinato]zinc(II) symbolized by 4α-[Zn(TAzPP)] (4), using the click chemistry approach in the presence of copper iodide. All of the synthetic porphyrin species reported herein were fully characterized by elemental analysis, infrared spectroscopy, proton nuclear magnetic resonance, UV-visible spectroscopy, and fluorescence. To synthesize the 4α-[Zn(TAzPP)] complex (4), we produced 4α-Meso-tetra-o-nitrophenylporphyrin (H₂T_NO2PP) and 4α-meso-tetra-o-aminophenylporphyrin (4α-H₂TNH₂PP) (1) using known classic literature methods. This 4α atropisomer was converted to 4α-meso-tetra-o-azidophenylporphyrin (4α-H₂TN₃PP) (3) by reaction with sodium nitrite and sodium azide, and then it was metalated by Zn(II), leading to [4α-meso-tetra(2-azidophenyl)porphyrinate]zinc(II) (4α-[Zn(TN₃PP)]) (3). The click chemistry synthetic method was finally used to prepare 4α-[Zn(TAzPP)] (4). This new tetracoordinated zinc(II) porphyrin complex was prepared and characterized in order to: (i) produce a receptor for anion recognition and sensing application for Cl⁻ and Br⁻; (ii) study the catalytic decomposition of rhodamine B (RhB) and methyl orange (MO) dyes; and (iii) determine the electronic characteristics as a photovoltaic device. Complex (4) formed 1:1 complex stoichiometric species with chloride and bromide halides and the average association constants of the 1:1 addicts were ~ 10³. The photodecomposition of RhB and MO dyes in the presence of complex (4) as a catalyst and molecular oxygen showed that complex (4) presented a photodegradation yield of approximately 70% and could be reused for five successive cycles without any obvious change in its catalytic activity. The current-voltage characteristics and impedance spectroscopy measurements of complex (4) confirmed that our zinc(II) metalloporphyrin could be used as a photovoltaic device.

In search of robust catalysts for redox transformations such as the hydrogen evolution reaction (HER) or CO₂ to CO reduction, we stepped on the previously reported meso-tetrakis(3,4,5-trimethoxyphenyl)porphyrinato cobalt(II) complex [Co(TTMPP)]. We prepared [Co(TTMPP)] in good yields and characterized it by IR, UV-vis absorption, photoluminescence spectroscopy, and cyclic voltammetry (CV). The [Co(TTMPP)] was used as a homogeneous catalyst for the electrochemical formation of H₂ (HER) in DMF (N,N’-dimethylformamide)/TFA (trifluoroacetic acid) and DMF/EtN₃BF₄ solutions, with high faradic efficiencies (FE). Additionally, the reduction of CO₂ to CO in DMF under a CO₂ atmosphere was catalyzed in DMF/TFE (TFE = 2,2,2-trifluoroethanol) and DMF/PhOH with high FE and only traces of H₂ as a by-product. Turnover frequencies of 15.80 or 9.33 s⁻¹, respectively were determined from CV experiments or controlled potential electrolysis in the presence of 1eq. TFE. They were lower with PhOH as proton source with 13.85 or 8.31 s⁻¹, respectively. Further, [Co(TTMPP)] as a solid catalyst (suspension) allowed the photodecomposition of the organic dyes methylene blue (MB) and rhodamine B (RhB) using H₂O₂ under visible light irradiation. The photocatalyst was photostable over five cycles. A photocatalytic mechanism was proposed based on trapping experiments of reactive oxygen species.

The present work describes the preparation and characterization of a new cobalt(III) porphyrin coordination compound named (chlorido)(nicotinoylchloride)[meso-tetra(para-chlorophenyl)porphyrinato]cobalt(III) dichloromethane monosolvate with the formula [Co^III(TClPP)Cl(NTC)]·CH₂Cl₂ (4). The single-crystal X-ray molecular structure of 4 shows very important ruffling and waving distortions of the porphyrin macrocycle. The Soret and Q absorption bands of 4 are very red-shifted as a consequence of the very distorted porphyrin core. This coordination compound was also studied by fluorescence and cyclic voltammetry. The efficiency of our four porphyrinic compounds—the H₂TClPP (1) free-base porphyrin, the [Co^II(TClPP)] (2) and [Co^III(TClPP)Cl] (3) starting materials, and the new Co(III) metalloporphyrin [Co^III(TClPP)Cl(NTC)]·CH₂Cl₂ (4)—as catalysts in the photochemical degradation was tested on malachite green (MG) dye. The current voltage of complexes 3 and 4 was also studied. Electrical parameters, including the saturation current density (J_s) and barrier height (ϕ_b), were measured.

The meso-tetrakis(4-(trifluoromethyl)phenyl)porphyrinato cobalt(II) complex [Co(TMFPP)] was synthesised in 93% yield. The compound was studied by ¹H NMR, UV-visible absorption, and photoluminescence spectroscopy. The optical band gap Eg was calculated to 2.15 eV using the Tauc plot method and a semiconducting character is suggested. Cyclic voltammetry showed two fully reversible reduction waves at E_1/2 = −0.91 V and E_1/2 = −2.05 V vs. SCE and reversible oxidations at 0.30 V and 0.98 V representing both metal-centred (Co(0)/Co(I)/Co(II)/Co(III)) and porphyrin-centred (Por²⁻/Por⁻) processes. [Co(TMFPP)] is a very active catalyst for the electrochemical formation of H₂ from DMF/acetic acid, with a Faradaic Efficiency (FE) of 85%, and also catalysed the reduction of CO₂ to CO with a FE of 90%. Moreover, the two triarylmethane dyes crystal violet and malachite green were decomposed using H₂O₂ and [Co(TMFPP)] as catalyst with an efficiency of more than 85% in one batch.

A new heteroleptic ruthenium complex based on a 2,2′;6′,2′′‐terpyridine (tpy) and a thioether‐based tridentate ligand, btap (btap: 2,6‐bis(2‐thioanisyl)pyridine) was synthesized. Under visible light irradiation, this complex in solution in acetonitrile undergoes a photochemical ejection of the thioether ligand leading to [Ru(tpy)CH₃CN)₃]²⁺ and the free ligand. The reaction was monitored using NMR and UV‐Vis spectroscopies. This is very probably the first example of a tridentate ligand being expelled by the action of light.

A joined experimental and theoretical study for unravelling the source of a strong hypsochromism.