Thermal and Mechanochemical Syntheses of Luminescent Mononuclear Copper(I) Complexes

Liang, Panyi; Kobayashi, Atsushi; Hasegawa, Tatsuya; Yoshida, Masaki; Kato, Masako

doi:10.1002/ejic.201700734

Cited by 20 publications

(14 citation statements)

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“…In fact, the mechanochemical synthesis of luminescent Cu(I) complexes has been reported as an effective technique to minimize the use of a solvent as well as to shorten the reaction time and improve the yield. − However, most mechanochemical syntheses of luminescent Cu(I) complexes require an assisting solvent, while a washing process is necessary to remove the unreacted starting materials. We have previously reported a thermal synthesis without the use of an assisting solvent, which enabled us to synthesize luminescent Cu(I) complexes via the melting of organic ligands to effectively promote complex formation. , However, certain amounts of organic solvent were still necessary during the washing process. Thus, in this work, we have focused on thermally stable Cu(I) coordination polymers because of (1) the high thermal stability of the coordination polymers, which allowed the removal of any unreacted materials, mainly excess organic ligands, via evaporation by simple heating and (2) the wide tunability of the emission color, from blue to red, which was achieved in the coordination polymeric system [Cu 2 I 2 (PPh 3 )(L)] n (PPh 3 = triphenylphosphine, L = N -heteroaromatic organic linkers). − Herein, we report the completely solvent-free mechanochemical thermal synthesis of two simple Cu(I) coordination polymers [Cu 2 I 2 (3,3′-bpy)] n and [Cu 2 I 2 (4,4′-bpy)] n (Scheme , CuI-3 and CuI-4 , respectively; bpy = 3,3′- or 4,4′-bipyridine, respectively) with two isomeric bpy linkers.…”

Section: Introductionmentioning

confidence: 99%

Quantitative Solvent-Free Thermal Synthesis of Luminescent Cu(I) Coordination Polymers

et al. 2019

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The luminescent Cu(I) coordination polymers [Cu2I2(m,m′-bpy)] n (CuI- m; m,m′-bpy = m,m′-bipyridine; m = 3, 4) were successfully synthesized by the solvent-free thermal reaction of the metal salt CuI with the organic linkers m,m′-bpy. Powder X-ray diffraction analysis revealed that CuI-3 was immediately formed when a mixture of CuI and 3,3′-bpy was ground in a mortar at room temperature (20 °C). In contrast, a temperature >120 °C was required to synthesize the CuI-4 isomer, probably because of the higher melting point of the 4,4′-bpy linker. Although excess bpy linker was necessary to afford the CuI- m in high yield, the quantitative synthesis, without any purification processes, was successfully achieved by simple heating at 140 °C, whereby the excess bpy linker was thermally removed by evaporation. Single crystal X-ray structural analysis indicated that in CuI-3 the dinuclear {Cu2I2} rhombic cores were bridged by 3,3′-bpy linkers. A similar structure was observed for CuI-4; however, the intermolecular π–π stacking that was effective in CuI-4 was suppressed in CuI-3 because of the twisted configuration of the two pyridyl rings of the 3,3′-bpy linker. CuI-3 exhibited bright green emission with the maximum (λem) at 519 nm and a high emission quantum yield (Φ = 0.58) in the solid state at room temperature, in contrast to the weak red emission of CuI-4 (λem = 653 nm, Φ < 0.01). Emission decay analysis and density functional theory calculations suggested that the CuI- m emissions could be attributed to the delayed fluorescence from the metal-to-ligand charge-transfer excited state effectively mixed with the halide-to-ligand charge-transfer excited state.

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Section: Introductionmentioning

confidence: 99%

Quantitative Solvent-Free Thermal Synthesis of Luminescent Cu(I) Coordination Polymers

et al. 2019

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“…Pioneering investigations on the luminescence of mononuclear copper complexes of general formula [Cu(N^N)2] + , where N^N is a chelating diimine ligand such as substituted phenanthrolines, were reported by the group of McMillin [19], which unrevealed emission from an higher-lying 1 MCLT state in thermal equilibrium with 3 MLCT manifold, [20,21] as well as the excited state quenching process through D2 flattening and exciplex formation [22,23]. Recently, Kato and collaborators showed that simple TADF-active copper(I) halide complexes stabilized by triphenylphosphine ligand and various N-aromatic ligands can be efficiently prepared from inexpensive reagents via mechanochemical syntheses in a rather straightforward manner [24][25][26][27].…”

Section: Introductionmentioning

confidence: 99%

Copper(I) complexes with remotely functionalized phosphine ligands: Synthesis, structural variety, photophysics and effect onto the optical properties

Egly

Bissessar

Achard

et al. 2021

Inorganica Chimica Acta

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The synthesis, chemical and photophysical investigation of a series of eight novel copperhalide derivatives with different nuclearity is herein presented. One mononuclear copper(I) complex with formula [CuI(pyridine)(P)2], where P is a functionalized phosphine, six dinuclear derivatives bearing the rhombic {Cu2I2} subunits and with general formula [Cu(µ -I)(P)(N)]2 (N = pyridine, quinoline and 4-cyanopyridine) as well as one tetranuclear copperiodide clusters of general formula [Cu(µ -I)P]4 consisting of a cubane-like {Cu4X4} motif were straightforwardly prepared, also by means of mechano-chemical synthetic procedure.The phosphine ligands were prepared in excellent yield by using simple hydrophosphination reactions. For five of the investigated cuprous iodide derivatives their atom connectivity and solid-state crystalline packing was unambiguously confirmed by solving their single-crystal X-ray structure. All the investigated complexes resulted into photo-and thermally-stable luminescent species. In the solid state as microcrystalline powder samples, the complexes display intense photoluminescence ranging from the sky-blue to orange-red portion of the spectrum with PLQY values of 0.28-0.50 and 0.34-0.97 at room and low (77 K) temperature, respectively, depending on the nature of both the coordinated N-heteroaromatic ring and phosphine ligands. In spite of the remote location of the functionalization of the phosphine, profound effects are observed onto the solid-state emission properties highlighting the importance of microenvironment for the emitters in the aggregated phase.

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“…The requirement of using dry and degassed solvents under inert reaction conditions increases the complexity of the reaction, adding to the cost of the synthesis, and generates a larger environmental footprint. The recent renaissance of mechanochemistry as a powerful synthetic tool can be used to overcome these problems to synthesize high-value products and organometallic-based catalysts. − Such solid-state mechanochemical reactions also eliminate the need to find suitable solvents to dissolve the reagents and other issues normally associated with solubility, enabling a wider variety of reagents to be used as molecular precursors. In short, mechanochemistry removes the need for solvents and also shortens the reaction time, leading to it being a more efficient and less polluting process.…”

Section: Introductionmentioning

confidence: 99%

Postsynthetic Modification of Half-Sandwich Ruthenium Complexes by Mechanochemical Synthesis

Jia

Zhi

et al. 2021

Inorg. Chem.

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A mild and environmentally friendly method to synthesize half-sandwich ruthenium complexes through the Wittig reaction between an aldehyde-tagged half-sandwich ruthenium complex and phosphorus ylide mechanochemically is reported herein. The mechanochemical synthesis of valuable half-sandwich ruthenium complexes resulted in a fast reaction, good yield with simple workup, and the avoidance of harsh reaction conditions and organic solvents. The synthesized half-sandwich ruthenium complexes exhibited high catalytic activity for transfer hydrogenation of ketones using 2-propanol as the hydrogen source and solvent. Density functional theory was carried out to propose a mechanism for the transfer hydrogenation process. The modeling suggests the importance of the labile p-cymene ligand in modulating the reactivity of the catalyst.

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Thermal and Mechanochemical Syntheses of Luminescent Mononuclear Copper(I) Complexes

Cited by 20 publications

References 44 publications

Quantitative Solvent-Free Thermal Synthesis of Luminescent Cu(I) Coordination Polymers

Quantitative Solvent-Free Thermal Synthesis of Luminescent Cu(I) Coordination Polymers

Copper(I) complexes with remotely functionalized phosphine ligands: Synthesis, structural variety, photophysics and effect onto the optical properties

Postsynthetic Modification of Half-Sandwich Ruthenium Complexes by Mechanochemical Synthesis

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