Electronic excited states of arylphosphine complexes of copper(I) halides

Fife, Dennis J.; Moore, William M.; Morse, Karen W.

doi:10.1021/ic00179a016

Cited by 20 publications

(7 citation statements)

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“…All the complexes have similar features dominated by the absorption of the arylphopshine in the 250-300 nm as also supported by the comparison of the absorption spectrum of the precursor DPEPhosCu(ACN) 2 PF 6. 46 The ancillary ligands contribute as well as in the UV region while the shoulders at lower energies are due to the electronic transitions from the d-orbital of the metal centre to the π * of the ancillary ligand, 1 MLCT. Emission properties in solution have been studied at room temperature in oxygen-free CH 2 Cl 2 solution to avoid the quenching effect of O 2 , and are displayed in Figure 3.…”

Section: Resultsmentioning

confidence: 99%

Luminescent Neutral Cu(I) Complexes: Synthesis, Characterization and Application in Solution-Processed OLED

Bizzarri

Fléchon

Fenwick

et al. 2016

ECS J. Solid State Sci. Technol.

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Four novel neutral copper(I) compounds were prepared, based on the chelating phosphine bis(2-(diphenylphosphino)phenyl)ether, (DPEPhos), and a series of nitrogen-containing heterocycles as ancillary ligands. The optical properties can be tuned according to the ancillary ligand and their emissions at room temperature in aprotic solvent (CH 2 Cl 2 ) go from greenish blue to orange. Their photoluminescence in solid state is particularly attractive and make their employment in opto-electronic devices very appealing. In particular, the low-cost preparation method of solution-processed light emitting devices is suitable for copper(I) complexes. In order to choose a suitable device architecture, the electrochemical characteristics were investigated and the frontier orbitals values were determined. Preliminary results on solution-processed OLED are presented.Organic Light-Emitting Devices, OLEDs, have attracted attention for several years. Indeed their applications are various, 1-3 ranging from full color flat panel display and lighting (white light), to micro-led and polarized light. The low power dissipation and high performances make them of great interest and opportunities for mobile applications and bendable displays. In order to gain the maximum luminous efficiency in optoelectronic devices, phosphorescent emitters are known to be the best material to be employed in device fabrication, 4-6 since the singlets and triplets excited states are randomly populated upon electric excitation. Currently the phosphorescent compounds that allow to fabricate highly efficient devices, are mainly based on the transition metal complexes, such as Ir(III), Ru(II), Os(II) and Pt(II) complexes. 7 Nowadays the growing OLED technology and the increasing demand of highly efficient and low power consumption devices draw the interest and efforts of both academic and companies. The ambitious goal is to employ low cost, abundant materials, and for these reasons photoluminescent Cu(I) complexes have recently gained increasing attention. Moreover Cu ions are much less toxic than the other employed heavy metals. Generally, these complexes are characterized by the Cu(I) metal core tetracoordinated in a pseudotetrahedral geometry. 8 In its oxidative state +1, copper has the d-orbitals completely filled and the electronic distribution of the charge is almost symmetrically localized around the metal centre, which favors a tetrahedral disposition of the ligands. The electronic transition d-d are then avoided and the luminescence comes from the triplet metal-toligand charge-transfer ( 3 MLCT) states, as long as the empty π orbitals are easily accessible in the ligands. 9 For this reason, closed shell d 10 copper(I) complexes do not suffer from the deactivation of MLCT by metal centred (MC) transitions, as might be the case for Ru(II) or other d 6 metal complexes. 10 However, undesired non-radiative pathways are nevertheless favored by vibrational modes and distortions of the tetrahedral conformation, in the excited state, which can be caused by flatt...

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Section: Resultsmentioning

confidence: 99%

Luminescent Neutral Cu(I) Complexes: Synthesis, Characterization and Application in Solution-Processed OLED

Bizzarri

Fléchon

Fenwick

et al. 2016

ECS J. Solid State Sci. Technol.

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“…Some differences are noted and need to be rationalized. Numerous mononuclear Cu(I) phosphine complexes have been investigated in the literature for their luminescence properties and their photosensitizing activities in relation to solar energy storage . For instance, the photoassisted conversion of norbornadiene into quadricyclane has been extensively investigated as a function of various Cu(I) phosphine complexes.…”

Section: Resultsmentioning

confidence: 99%

Theoretical Study and Luminescence Properties of the Cyclic Cu₃(dppm)₃OH²⁺ Cluster. The First Luminescent Cluster Host at Room Temperature

Provencher

Harvey

1996

Inorg. Chem.

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The [Cu(3)(dppm)(3)OH](BF(4))(2) cyclic cluster host is found to be luminescent at 298 K (lambda(max) = 540 nm; tau(e) = 89 +/- 9 &mgr;s; Phi(e) = 0.14 +/- 0.01) in degassed ethanol solutions and at 77 K (lambda(max) = 480 nm; tau(e) = 170 +/- 40 &mgr;s; Phi = 0.73 +/- 0.07) also in ethanol. The nature of the lowest energy excited states has been addressed theoretically using density functional theory and experimentally using UV-visible, luminescence, and polarized luminescence spectroscopy and is found to be (1,3)A(2) arising from the.(18e)(4)(7a(2))(1)(13a(1))(1) electronic configuration. The excited state geometry optimization for the model Cu(3)(PH(3))(6)OH(2+) compound in its T(1) state ((3)A(2)) has been performed using density functional theory and compared to its ground state structure. The Cu.Cu bond length is expected to decrease greatly in the excited state (calculated DeltaQ approximately 0.47 Å), in agreement with the d(10) electronic configuration. The perturbation of the photophysical properties by the addition of two guest carboxylate anions has been investigated. From the Stern-Volmer plots, the quenching constants, k(q), are 1.65 x 10(8) and 5.10 x 10(8) M(-)(1) s(-)(1) for acetate and 4-aminobenzoate, respectively, which are also proportional to the relative binding strengths of the substrates with Cu(3)(dppm)(3)OH(2+) (i.e., acetate < 4-aminobenzoate).

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“…The 77 K luminescence of PPh 3 , in fact, is centered at 445 nm with a lifetime of 13.6 ms and is attributed to phosphorescence. 31 The spectral features and the lifetimes, on the order of 200 ms, of the luminescence of the complexes at 77 K, suggest a ligand contribution to the emission, that can be tentatively assigned to a mixed MLCT/LC (ligand-centered) phosphorescence. A similar long-lived blue emission in solution at 77 K has been recently reported for Ag(I)-bis(diphosphine) complexes, and has been attributed to 3 MLCT/ 3 IL (intra-ligand) states based on tetrahedral geometry.…”

Section: Photophysical Propertiesmentioning

confidence: 93%

Polymorph and isomer conversion of complexes based on CuI and PPh₃easily observed via luminescence

et al. 2012

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Reactions between copper(I) iodide and triphenylphosphine have been explored in solution and in the solid state and six luminescent coordination complexes have been obtained and characterized by X-ray diffraction and UV-vis spectroscopy and photophysics. Solid-state reactions of CuI with PPh(3) in different conditions (kneading, vapour digestion) and stoichiometries resulted in the formation of high ratio ligand:metal compounds while tetrameric structures could be obtained only by solution reactions. Crystal structures were determined by single crystal X-ray diffraction while purity of the bulk product was checked by powder diffraction (XRPD). Three different tetrameric structures with 1:1 stoichiometry have been synthesized: two closed cubane-type polymorphs [CuI(PPh(3))](4) (form 1a) and [CuI(PPh(3))](4) (form 1b) and an open step-like isomer [CuI(PPh(3))](4) (form 2). The conversions between the polymorphs and isomers have been studied and characterized by XRPD. The most stable form [CuI(PPh(3))](4) (form 1b) can convert into the open step-like isomer [CuI(PPh(3))](4) (form 2) in a slurry experiment with EtOH or CH(2)Cl(2) or AcCN and converts back into [CuI(PPh(3))](4)1b when exposed to vapors of toluene. At room temperature all the tetrameric compounds exhibit luminescence in the solid state and, notably, the two polymorphs show a dissimilar dual emission at low temperature. The luminescence features in the solid state seem to be peculiarly related to the presence of the aromatic phosphine ligand and depend on the Cu-Cu distance in the cluster.

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Electronic excited states of arylphosphine complexes of copper(I) halides

Cited by 20 publications

References 0 publications

Luminescent Neutral Cu(I) Complexes: Synthesis, Characterization and Application in Solution-Processed OLED

Luminescent Neutral Cu(I) Complexes: Synthesis, Characterization and Application in Solution-Processed OLED

Theoretical Study and Luminescence Properties of the Cyclic Cu₃(dppm)₃OH²⁺ Cluster. The First Luminescent Cluster Host at Room Temperature

Polymorph and isomer conversion of complexes based on CuI and PPh₃easily observed via luminescence

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Electronic excited states of arylphosphine complexes of copper(I) halides

Cited by 20 publications

References 0 publications

Luminescent Neutral Cu(I) Complexes: Synthesis, Characterization and Application in Solution-Processed OLED

Luminescent Neutral Cu(I) Complexes: Synthesis, Characterization and Application in Solution-Processed OLED

Theoretical Study and Luminescence Properties of the Cyclic Cu3(dppm)3OH2+ Cluster. The First Luminescent Cluster Host at Room Temperature

Polymorph and isomer conversion of complexes based on CuI and PPh3easily observed via luminescence

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Theoretical Study and Luminescence Properties of the Cyclic Cu₃(dppm)₃OH²⁺ Cluster. The First Luminescent Cluster Host at Room Temperature

Polymorph and isomer conversion of complexes based on CuI and PPh₃easily observed via luminescence