Subtle Modulation of Cu4X4L2 Phosphine Cluster Cores Leads to Changes in Luminescence

Chen, Kelly; Shearer, Jason; Catalano, Vincent J.

doi:10.1021/acs.inorgchem.5b00443

Cited by 56 publications

(60 citation statements)

References 58 publications

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“…The synthesis only failed for tris-( pentafluorophenyl)phosphine as ancillary ligand. Probably the donor properties of the lone pair of the phosphine are reduced due to the strong electron-withdrawing properties of the fluorines, leading to the tetranuclear structure, a Cu 4 I 4 unit bridged two times by the PyrPhos ligand, described already by Chen et al 48…”

Section: Synthesismentioning

confidence: 91%

Highly soluble fluorine containing Cu(i) AlkylPyrPhos TADF complexes

et al. 2019

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Luminescent Cu(I) AlkylPyrPhos complexes with a butterfly-shaped Cu 2 I 2 core and halogen containing ancillary ligands, with a special focus on fluorine, have been investigated in this study. These complexes show extremely high solubilities and a remarkable ( photo)chemical stability in a series of solvents. A tunable emission resulting from thermally activated delayed fluorescence with high quantum yields was determined by luminescence and lifetime investigations in solvents and solids. Structures of the electronic ground states were analyzed by single crystal X-ray analysis. The structure of the lowest excited triplet state was determined by transient FTIR spectroscopy, in combination with quantum chemical calculations. With the obtained range of compounds we address the key requirement for the production of organic light emitting diodes based on solution processing. † Electronic supplementary information (ESI) available. CCDC 1919266-1919270, 1918364 and 1919271-1919273. For ESI and crystallographic data in CIF or other electronic format see

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Section: Synthesismentioning

confidence: 91%

Highly soluble fluorine containing Cu(i) AlkylPyrPhos TADF complexes

et al. 2019

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“…As with cubane structures supported by heterodonor ligands, Jessop and co‐workers have reported a Cu 4 Br 4 cubane structure supported by phosphaamidine with spectator imine arms . Catalano and co‐workers have reported flexible Cu 4 X 4 parallelogram and butterfly structures bearing the heterodonor ligand 2‐(diphenylphosphino)pyridine . However, to the best of our knowledge, heterodonor ligands supported symmetrical and asymmetrical binuclear, and cubane type Cu(I) complexes with fluxional properties have not been reported to date.…”

Section: Introductionmentioning

confidence: 99%

Synthesis, X‐Ray Structures, and Fluxional Properties of Symmetrical, Asymmetrical Binuclear and Cubane Type Copper(I) Complexes Bearing the Pyrrole‐Based P, N‐Hetero Donor Ligand

et al. 2020

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The 1 : 1 reaction between 2-(3,5-dimethylpyrazolylmethyl)-5-(diphenylphosphinomethyl)pyrrole L and CuX (X = Cl, and Br) in THF afforded the symmetrical binuclear copper(I) complexes [Cu(μ-X){μ-C 4 H 2 NH-2-(CH 2 PPh 2 )-5-(CH 2 Me 2 pz)-k 2 P,N}] 2 , having one type of copper environment. When X = I, the asymmetrical complex having two copper environments was isolated, in addition to the symmetrical complex as crystals. Interestingly, the 1 : 2 ratio reaction between L and CuCl gave a distorted cubane type complex [Cu 4 Cl 4 {μ-C 4 H 2 NH-2-(CH 2 PPh 2 )-5-(CH 2 Me 2 pz)-k 2 P,N} 2 ], while the CuBr and CuI reactions did not give similar cubane complexes. Conversely, the 2 : 1 (L : Cu) ratio reactions using CuX (X=Cl, Br and I) in THF suggest the formation of four coordinate bis-chelated copper(I) complex of the type [CuL 2 ] + in solution, in addition to the binuclear complexes. The X-ray solid state structures of [CuL 2 X 2 ] (X = Br and I) are retained in solution, in contrast to its chloride derivative giving two signals in 31 P{ 1 H} NMR spectrum. The formation of the binuclear complexes from [CuL 2 ] + and their equilibria were shown by variable temperature NMR, 31 P{ 1 H} 2D NOESY and HRMS studies. In addition, the reaction of L with [Cu(CH 3 CN) 4 ]BF 4 gave yet another binuclear complex [Cu 2 L 2 ] [BF 4 ] 2 which was characterized by spectroscopic methods. This study lends support for the hemilability of L. Figure 5. (a) Variable-temperature 1 H NMR spectra (400 MHz) of complex 4 in CDCl 3 ; (b) proposed dynamic process in solution. ChemistrySelectFull Papers

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“…Pyridylphosphines often stabilize these copper halide clusters by the P,N‐coordination , . Moreover the pyridyl group coordinated to the copper metal core is involved in the luminescent transitions.…”

Section: Introductionmentioning

confidence: 99%

Pyridyl Containing 1,5-Diaza-3,7-diphosphacyclooctanes as Bridging Ligands for Dinuclear Copper(I) Complexes

Strelnik

Musina

Ignatieva

et al. 2017

Z. Anorg. Allg. Chem.

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1,5-bis(R)-3,7-bis[2-(pyridine-2Ј-yl)ethyl)-1,5-diaza-3,7-diphosphacyclooctanes 1 and 2 and their copper(I) complexes 3 and 4 were developed. The butterfly-shaped copper-iodide core and unusual P,N-chelate and P,P-bridged coordination mode of the heterocyclic ligand in the dinuclear complexes 3 and 4 were revealed. Complexes 3 895 and 4 display emission in green range of spectra, with lifetimes in a microsecond domain and quantum yields of luminescence in solidstate up to 38 %. Thermochromic effects found for the phosphorescence of 4 in solutions are ascribed to rigidochromism.

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Subtle Modulation of Cu₄X₄L₂ Phosphine Cluster Cores Leads to Changes in Luminescence

Cited by 56 publications

References 58 publications

Highly soluble fluorine containing Cu(i) AlkylPyrPhos TADF complexes

Highly soluble fluorine containing Cu(i) AlkylPyrPhos TADF complexes

Synthesis, X‐Ray Structures, and Fluxional Properties of Symmetrical, Asymmetrical Binuclear and Cubane Type Copper(I) Complexes Bearing the Pyrrole‐Based P, N‐Hetero Donor Ligand

Pyridyl Containing 1,5-Diaza-3,7-diphosphacyclooctanes as Bridging Ligands for Dinuclear Copper(I) Complexes

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