Highly luminescent copper(<scp>i</scp>) halide complexes chelated with a tetradentate ligand (PNNP): synthesis, structure, photophysical properties and theoretical studies

Jia, Ji-Hui; Chen, Xulin; Liao, Jian-Zhen; Liang, Dong; Yang, Mingxue; Yu, Rongmin; Lu, Can‐Zhong

doi:10.1039/c8dt03452d

Cited by 41 publications

(19 citation statements)

References 51 publications

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“…Dinuclear Cu(I) cores possess a great advantage over mononuclear core since they have a rigid structure and thus high efficiency recorded for bulky ligand chelated complexes. − However, the reported dinuclear Cu(I) halide complexes are mainly limited to bidendate diphoshines ,− or imine and phosphine ,− ,− ligands, whereas bidentate amine and phosphine ligands are rarely reported. In comparison to the great success in green emitters, it seems that blue emitters are still a challenge to meet the requirement of full color displays and white light sources. , …”

Section: Introductionmentioning

confidence: 99%

Largely Color-Tuning Prompt and Delayed Fluorescence: Dinuclear Cu(I) Halide Complexes with tert-Amines and Phosphines

Chen

Yang

et al. 2021

Inorg. Chem.

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Luminescent copper(I) halide complexes with bi- and tridentate rigid ligands have gained wide research interests. In this paper, six tetracoordinate dinuclear copper(I) halide complexes, Cu2X2(ppda)2 [ppda = 2-[2-(dimethylamino)phenyl(phenyl)phosphino]-N,N-dimethylaniline, X = I (1), Br (2), Cl (3)] and Cu2X2(pfda)2 [pfda = 2-[2-(dimethylamino)-4-(trifluoromethyl)phenyl(phenyl)phosphino]-N,N-dimethyl-5-trifluoromethylaniline, X = I (4), Br (5), Cl (6)], were successfully prepared and systematically characterized on their structures and photophysical properties. Complexes 1–5 have a centrosymmetric form with a planar Cu2X2 unit, and complex 6 has a mirror symmetry form with a butterfly-shaped Cu2X2. Solid complexes 1, 4, and 5 emit delayed fluorescence at room temperature, intense blue to greenish yellow (λmax = 443–570 nm) light, and their peak wavelengths are located at 443–570 nm with microsecond lifetimes (τ = 0.4–19.2 μs, ΦPL = 0.05–0.48). Complexes 2, 3, and 6 show prompt fluorescence, very weak yellowish green to yellow (λmax = 534–595 nm) emission with peak wavelengths at 534–595 nm, and lifetimes in nanoseconds (τ = 4.4–9.3 ns, ΦPL < 0.0001). (Metal + halide) to ligand and intraligand charge transitions are the main origin of the emission of the complexes. Solution-processed, complex-4-based nondoped and doped devices emit yellow green light with CIE coordinated at (0.41, 0.51), a maximum EQE up to 0.17%, and luminance reaching 75.52 cd/m2.

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Section: Introductionmentioning

confidence: 99%

Largely Color-Tuning Prompt and Delayed Fluorescence: Dinuclear Cu(I) Halide Complexes with tert-Amines and Phosphines

Chen

Yang

et al. 2021

Inorg. Chem.

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“…Since the efficient organic-light emitting diodes (OLEDs) and light-emitting electrochemical cells (LEECs) based on Cu(I) complexes were reported by Wang group and Armaroli group (Zhang et al, 2004; Armaroli et al, 2006), respectively, luminescent Cu(I) complexes have been attracting considerable attention as the emitting materials for electroluminescent (EL) devices (Volz et al, 2014; Gneuß et al, 2015; Hofbeck et al, 2015; Kobayashi et al, 2016; Brunner et al, 2017; He et al, 2017; Huang et al, 2017; Su et al, 2017; Brown et al, 2018; Mohankumar et al, 2018; Schinabeck et al, 2018; Jia et al, 2019). According to the recent reports, most of Cu(I) complexes show thermally activated delayed fluorescence (TADF) due to small energy gaps (Δ E ST ) between the lowest singlet state (S 1 ) and the lowest triplet states (T 1 ) (Gneuß et al, 2015; Hofbeck et al, 2015; Kobayashi et al, 2016; Brunner et al, 2017; Huang et al, 2017; Su et al, 2017; Mohankumar et al, 2018; Schinabeck et al, 2018; Jia et al, 2019). As we all know, singlet and triplet excitons are formed in a ratio of 1:3 during EL device operation.…”

Section: Introductionmentioning

confidence: 99%

Synthesis, Structures, and Photophysical Properties of Novel Four-Coordinate Cu(I) Complexes Supported by Chelating N-Heterocyclic Carbene Ligands

Wang

Sun

et al. 2019

Front. Chem.

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Luminescent Cu(I) complexes are promising emitting materials for electroluminescent devices due to their low cost and abundant resources, as well as high emission efficiency. It is well-known that N-heterocyclic carbenes (NHCs) are excellent ligands for transition metal complexes. To investigate the photophysical properties of Cu(I)-NHC complexes, a series of new mononuclear four-coordinate Cu(I) complexes supported by the diphosphine ligand bis[2-(diphenylphosphino)phenyl]ether (POP) and the NHC ligands, consisting of imidazolylidene and pyrimidine units, were synthesized and fully characterized. To tune the photophysical properties of these Cu(I)-NHC complexes, the NHC ligands were attached with electron-withdrawing/donating groups (fluorine, chlorine, methyl and methoxyl) at the pyrimidine unit. All of these Cu(I)-NHC complexes adopt the typical distorted tetrahedral configuration. The electron-donating groups can lead to shorter Cu–N bond distances and longer Cu–C bond distances compared to the electron-withdrawing groups. Theoretical calculation results show that the highest occupied molecular orbitals are mainly distributed on the Cu(I) ion, POP, and carbene unit, while the lowest unoccupied molecular orbitals are mostly located on the pyrimidine unit of NHC ligands. The lowest energy electronic transitions of these Cu(I)-NHC complexes are mainly the metal-to-ligand charge transfer transition and ligand-to-ligand charge transfer transition. These Cu(I)-NHC complexes in solid state show tunable emissions from 530 to 618 nm with efficiencies of 0.5–38.1% at room temperature. The photophysical behaviors of these complexes at 298 and 50 K match well with the thermally activated delayed fluorescence (TADF) characteristics.

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“…As a result, the copper complex bridged by I À anions forms a planar rhombic Cu 2 I 2 structure. [20] Similar to the mononuclear complexes, the CuÀ N bond distance (2.133(2) Å) of (CuL4I) 2 is a little shorter than that of (CuL1I) 2 (2.210(2) Å). The CuÀ Cu distances in (CuL1I) 2 and (CuL4I) 2 are 2.7268( 12) Å and 2.8689(17) Å, respectively, which approximate to the sum of the van der Waals radius of copper (2.80 Å).…”

Section: Synthesis and Structuresmentioning

confidence: 82%

Luminescent mono‐and dinuclear copper(I) complexes based on bulky bisphosphino‐substituted benzimidazole derivatives

Liu

et al. 2021

Zeitschrift anorg allge chemie

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Four mono-and two dinuclear Cu(I) complexes were synthesized based on novel 4-diphenylphosphino-benzimidazole (P^N) derivatives, and their structures as well as photophysical properties were systematically investigated. X-ray crystallographic analysis reveals that the Cu(I) centers adopt pseudotetrahedral geometries. All the complexes in powder at 293 K display bright phosphorescence with the highest photolumines-cent quantum yield of 37.6 %. The emission maxima could be finely tuned from 514 to 592 nm by the methoxy substituent on the N^P ligands. The combined experimental results at different temperature (293 K and 77 K) and theoretical studies suggest that the nature of the emissive states can be mainly assigned as a dominant charge-transfer character involving major components of 3 (M + X) LCT transitions.

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Highly luminescent copper(i) halide complexes chelated with a tetradentate ligand (PNNP): synthesis, structure, photophysical properties and theoretical studies

Abstract: Strongly emissive copper(i) halide complexes constructed from a new tetradentate chelating ligand and butterfly-shaped Cu2X2 cores are presented and systematically investigated.

Cited by 41 publications

References 51 publications

Largely Color-Tuning Prompt and Delayed Fluorescence: Dinuclear Cu(I) Halide Complexes with tert-Amines and Phosphines

Largely Color-Tuning Prompt and Delayed Fluorescence: Dinuclear Cu(I) Halide Complexes with tert-Amines and Phosphines

Synthesis, Structures, and Photophysical Properties of Novel Four-Coordinate Cu(I) Complexes Supported by Chelating N-Heterocyclic Carbene Ligands

Luminescent mono‐and dinuclear copper(I) complexes based on bulky bisphosphino‐substituted benzimidazole derivatives

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