Mononuclear and dinuclear heteroleptic Cu(I) complexes based on pyridyl-triazole and DPEPhos with long-lived excited-state lifetimes

Bizzarri, Claudia; Arndt, Andreas P.; Kohaut, Stephan; Fink, Karin; Nieger, Martin

doi:10.1016/j.jorganchem.2018.07.013

Cited by 14 publications

(29 citation statements)

References 54 publications

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“…Needle-shaped crystals of 5b were obtained by the slow diffusion of cyclohexane into a concentrated solution in dichloromethane. The molecular structure of complex 5b was determined by X-ray diffraction, shown in Figure 3 , and agrees with heteroleptic Cu(I) complexes with similar ligands [ 40 , 41 ]. Bond valence sum analysis for Cu(1) in 5b gave a calculated oxidation state of 1.007 [ 42 ].…”

Section: Resultssupporting

confidence: 55%

“…The low emission of Cu(I) complexes even in non-coordinating solvents, such as DCM, is attributed to the Jahn-Teller distortion that the complex undergoes upon excitation. The presence of the methyl substituent α to the pyridine might have impeded the distortion to some extent, as this was also demonstrated in other studies [40,[59][60][61]. Complex 5c presents a Φ of only 0.9%.…”

Section: In Solutionsupporting

confidence: 64%

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Cyan-Emitting Cu(I) Complexes and Their Luminescent Metallopolymers

et al. 2021

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Copper complexes have shown great versatility and a wide application range across the natural and life sciences, with a particular promise as organic light-emitting diodes. In this work, four novel heteroleptic Cu(I) complexes were designed in order to allow their integration in advanced materials such as metallopolymers. We herein present the synthesis and the electrochemical and photophysical characterisation of these Cu(I) complexes, in combination with ab initio calculations. The complexes present a bright cyan emission (λem ~ 505 nm) in their solid state, both as powder and as blends in a polymer matrix. The successful synthesis of metallopolymers embedding two of the novel complexes is shown. These copolymers were also found to be luminescent and their photophysical properties were compared to those of their polymer blends. The chemical nature of the polymer backbone contributes significantly to the photoluminescence quantum yield, paving a route for the strategic design of novel luminescent Cu(I)-based polymeric materials.

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Section: Resultssupporting

confidence: 55%

Section: In Solutionsupporting

confidence: 64%

Cyan-Emitting Cu(I) Complexes and Their Luminescent Metallopolymers

et al. 2021

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“…This lability is correlated to the increased flexibility of NN, due to the presence of the methylene spacer between the quino(xa)line and triazole units, affecting the easiness of ligand exchange. Therefore, a comparison was done for the bond lengths and bite angles between complexes 1 – 4 and previously published Cu‐complexes with a related structure R 1 [11b] and R 2 [11a] ( cf . Figure 2) .…”

Section: Resultsmentioning

confidence: 99%

“…Although complexes 1 – 3 show negligible difference in bond lengths (Δ<0.06 Å), more significant differences are associated with the NN bite angles N 2 ‐Cu−N 4 (ca. 10°) in respect to R 1 [11b] and R 2 [11a] (Table 1).…”

Section: Resultsmentioning

confidence: 99%

Versatile Heteroleptic Cu(I) Complexes Based on Quino(xa)‐line‐Triazole Ligands: from Visible‐Light Absorption and Cooperativity to Luminescence and Photoredox Catalysis

et al. 2021

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Four new heteroleptic Cu(I) complexes based on 1, 2, 3‐triazolyl‐quinoline or quinoxaline and a chelating diphosphine were prepared and fully characterised. The mononuclear derivatives absorb in the visible region, up to 600 nm, while the dinuclear complex has a long‐tail absorption up to 800 nm, showing an additional electronic state corroborated by theoretical calculations. Although a methylene group between the triazole and the quino(xa)line moiety increases the bite angle and decreases the luminescence in solution, all complexes emit brightly in the solid‐state. Their redox properties in the excited state were determined, proving their ability in serving as photoredox catalysts in atom transfer radical addition successfully.

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“…[24] However, recent research has found that some dinuclear copper(I) complexes possess a more rigid molecular conformation and a smaller S1-T1 energy gap than mononuclear analogues, which would result in high PL and EL efficiencies. [25][26][27] Moreover, introduction of another metal atom can effectively enhance the SOC and further realize phosphorescence emission. [24] In pursuit of novel [Cu 2 (N N) 2 (P P) 2 ] 2 + complexes, we choose diphosphine compounds (Xantphos, Dppp and Binap) as the P P ligand, and N,N-diethylaniline-bridged triazol-pyridine (BPTA) as the N N ligand.…”

Section: Introductionmentioning

confidence: 99%

Three Luminescent Dinuclear Copper(I) Complexes with P˄N Ligands: Synthesis, Photophysical Properties, DFT Calculations and AIE Behavior

Dou

Xiao

et al. 2021

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Three new BPTA-bridged binuclear copper(I) complexes bearing three different diphosphine ligands, namely, [(Cu I ) 2 (Xantphos) 2 (BPTA)](BF 4 ) 2 (Cu1), [(Cu I ) 2 (Dppp) 2 (BPTA)](BF 4 ) 2 (Cu2), and [(Cu I ) 2 (Binap) 2 (BPTA)](BF 4 ) 2 (Cu3), have been synthesized and characterized. The X-ray structure analyses of complex Cu3 show that the central copper(I) ion adopts a distorted tetrahedral geometry. Complexes Cu1 and Cu2 exhibit greenish-yellow emission with excited-state lifetime (13μs and 27μs) and photoluminescence quantum yields (6.86 % and 0.62 %) at room temperature in the solid state. Emission decay measurement and theoretical calculation suggest that the transition nature of their emission could be assigned to 3 MLCT/ 3 LC excited states. More interesting, complexes Cu1-Cu3 are weakly emissive in solution but become strongly luminescent in solid state, so it has the aggregation induced emission (AIE) behavior.

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Mononuclear and dinuclear heteroleptic Cu(I) complexes based on pyridyl-triazole and DPEPhos with long-lived excited-state lifetimes

Cited by 14 publications

References 54 publications

Cyan-Emitting Cu(I) Complexes and Their Luminescent Metallopolymers

Cyan-Emitting Cu(I) Complexes and Their Luminescent Metallopolymers

Versatile Heteroleptic Cu(I) Complexes Based on Quino(xa)‐line‐Triazole Ligands: from Visible‐Light Absorption and Cooperativity to Luminescence and Photoredox Catalysis

Three Luminescent Dinuclear Copper(I) Complexes with P˄N Ligands: Synthesis, Photophysical Properties, DFT Calculations and AIE Behavior

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