Structural forms in complexes of 2,9-dimethyl-1,10-phenanthroline with simple salts of copper(I) and other univalent ‘closed shell’ species

Mutrofin, Siti; Chan, Eric J.; Healy, Peter Conrad; Marinelli, Alessandro; Ngoune, Jean; Pettinari, Cláudio; Pettinari, Riccardo; Somers, Neil; Skelton, Brian W.; White, and Andrew J. P.

doi:10.1016/j.ica.2007.11.009

Cited by 11 publications

(9 citation statements)

References 27 publications

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“…The [Cu(P^P)(dmphen)]BF 4 complexes were obtained through sequential ligand substitution of [Cu(NCMe) 4 ]BF 4 with the diphosphine ligands L1 – L7 , followed by dmphen in a 1:1:1 ratio in DCM and/or MeCN, following protocols previously reported in the literature. , Complexes 1 and 2 have been previously reported, and our characterization data match the known data. , The formation of a small proportion (2–10% of the crude product) of the homoleptic product [Cu(dmphen) 2 ]BF 4 was evident by 1 H NMR. This byproduct proved difficult to remove by column chromatography, but purification could be achieved through recrystallization from DCM/ether to afford orange/yellow/red crystals of heteroleptic complexes of [Cu(P^P)(dmphen)]BF 4 in high yields (80–96%; Scheme ).…”

Section: Resultssupporting

confidence: 67%

“…18,53 Complexes 1 and 2 have been previously reported, and our characterization data match the known data. 53,54 The formation of a small proportion (2−10% of the crude product) of the homoleptic product [Cu(dmphen) 2 ]BF 4 55 was evident by 1 H NMR. This byproduct proved difficult to remove by column chromatography, but purification could be achieved through recrystallization from DCM/ether to afford orange/yellow/red crystals of heteroleptic complexes of [Cu(P^P)(dmphen)]BF 4 in high yields (80−96%; Scheme 2).…”

Section: ■ Results and Discussionmentioning

confidence: 99%

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Wide-Bite-Angle Diphosphine Ligands in Thermally Activated Delayed Fluorescent Copper(I) Complexes: Impact on the Performance of Electroluminescence Applications

Mackenzie

Said

et al. 2021

Inorg. Chem.

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We report a series of seven cationic heteroleptic copper(I) complexes of the form [Cu(P^P)(dmphen)]BF 4 , where dmphen is 2,9-dimethyl-1,10-phenanthroline and P^P is a diphosphine chelate, in which the effect of the bite angle of the diphosphine ligand on the photophysical properties of the complexes was studied. Several of the complexes exhibit moderately high photoluminescence quantum yields in the solid state, with Φ PL of up to 35%, and in solution, with Φ PL of up to 98%. We were able to correlate the powder photoluminescence quantum yields with the % V bur of the P^P ligand. The most emissive complexes were used to fabricate both organic lightemitting diodes and light-emitting electrochemical cells (LECs), both of which showed moderate performance. Compared to the benchmark copper(I)-based LECs, [Cu(dnbp)(DPEPhos)] + (maximum external quantum efficiency, EQE max = 16%), complex 3 (EQE max = 1.85%) showed a much longer device lifetime (t 1/2 = 1.25 h and >16.5 h for [Cu(dnbp)(DPEPhos)] + and complex 3, respectively). The electrochemiluminescence (ECL) properties of several complexes were also studied, which, to the best of our knowledge, constitutes the first ECL study for heteroleptic copper(I) complexes. Notably, complexes exhibiting more reversible electrochemistry were associated with higher annihilation ECL as well as better performance in a LEC.

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Section: Resultssupporting

confidence: 67%

Section: ■ Results and Discussionmentioning

confidence: 99%

Wide-Bite-Angle Diphosphine Ligands in Thermally Activated Delayed Fluorescent Copper(I) Complexes: Impact on the Performance of Electroluminescence Applications

Mackenzie

Said

et al. 2021

Inorg. Chem.

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“…4,16,20−28 In the ground state, [Cu(I)(dmp) 2 ] + adopts a pseudo tetrahedral coordination with D 2d symmetry. The lowest energy visible absorption bands of [Cu(I)(dmp) 2 ] + correspond to MLCT transitions; upon excitation, one of the d electrons of the copper is transferred to the phenanthroline ligands, converting the copper center from a Cu(I) 3d 10 to a Cu(II) 3d 9 configuration. The now asymmetrically occupied copper center undergoes a secondorder, pseudo Jahn−Teller distortion, causing the molecule to flatten into a D 2 geometry, which decreases the angle between the two phenanthroline ligand planes.…”

Section: Introductionmentioning

confidence: 99%

Effects of Electronic and Nuclear Interactions on the Excited-State Properties and Structural Dynamics of Copper(I) Diimine Complexes

Mara

Jackson

Huang³

et al. 2013

J. Phys. Chem. B

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The effects of structural constraints on the metal-to-ligand charge transfer (MLCT) excited state structural dynamics of cuprous bis-2,9-diphenyl-phenanthroline ([Cu(I)(dpp)(2)](+)) in both coordinating acetonitrile and noncoordinating toluene were studied using X-ray transient absorption (XTA) spectroscopy and density functional theory (DFT) calculations. The phenyl groups attached to the phenanthroline ligands not only effectively shield the Cu(I) center from solvent molecules, but also force a flattened tetrahedral coordination geometry of the Cu(I) center. Consequently, the MLCT state lifetime in [Cu(I)(dpp)(2)](+) is solvent-independent, unlike the previously studied 2,9-methyl substituted bis-phenanthroline Cu(I) complex. The MLCT state of [Cu(I)(dpp)(2)](+) still undergoes a "pseudo Jahn-Teller distortion," with the angle between the two phenanthroline ligand planes decreased further by 7°. The XTA results indicate that, in the MLCT excited state of [Cu(I)(dpp)(2)](+), the phenyls at the 2, 9 positions of the phenanthroline rotate, breaking the π-π interaction with the phenanthroline ligands without ever rotating in-plane with the phenanthroline ligands. Hence, the transferred electron density from the Cu(I) center is localized on the phenanthroline moiety with no charge density present on the phenyl rings. The insight about the effect of the structural constraints on the MLCT state properties will guide the design of Cu(I) diimine complexes with suitable excited-state properties to function as earth-abundant dye sensitizers for solar electricity generation.

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“…The photoexcited states of transition metal complexes have important functions in solar energy conversion applications. In spite of their strong absorption in the visible spectrum and their ability to donate electrons in light-induced electron-transfer reactions, excited metal-to-ligand-charge-transfer (MLCT) states of Cu(I) diimine complexes have not been as readily utilized in light-driven fuel and electricity generation processes − as their Ru(II), − Os(II), and Ir(III) counterparts. This is in part due to lingering questions about their structural reorganization, strong solvent dependent excited state dynamics, , low oxidation potential, , and the lability of Cu(II) complexes in the MLCT state.…”

Section: Introductionmentioning

confidence: 99%

Strong Steric Hindrance Effect on Excited State Structural Dynamics of Cu(I) Diimine Complexes

et al. 2012

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The metal-to-ligand-charge-transfer (MLCT) excited state of Cu(I) diimine complexes is known to undergo structural reorganization, transforming from a pseudotetrahedral D(2d) symmetry in the ground state to a flattened D(2) symmetry in the MLCT state, which allows ligation with a solvent molecule, forming an exciplex intermediate. Therefore, the structural factors that influence the coordination geometry change and the solvent accessibility to the copper center in the MLCT state could be used to control the excited state properties. In this study, we investigated an extreme case of the steric hindrance caused by attaching bulky tert-butyl groups in bis(2,9-di-tert-butyl-1,10-phenanthroline)copper(I), [Cu(I)(dtbp)(2)](+). The two bulky tert-butyl groups on the dtbp ligand lock the MLCT state into the pseudotetrahedral coordination geometry and completely block the solvent access to the copper center in the MLCT state of [Cu(I)(dtbp)(2)](+). Using ultrafast transient absorption spectroscopy and time-resolved emission spectroscopy, we investigated the MLCT state property changes due to the steric hindrance and demonstrated that [Cu(I)(dtbp)(2)](+) exhibited a long-lived emission but no subpicosecond component that was previously assigned as the flattening of the pseudotetrahedral coordination geometry. This suggests the retention of its pseudotetrahedral D(2d) symmetry and the blockage of the solvent accessibility. We made a comparison between the excited state dynamics of [Cu(I)(dtbp)(2)](+) with its mono-tert-butyl counterpart, bis(2-tert-butyl-1,10-phenanthroline)copper(I) [Cu(I)(tbp)(2)](+). The subpicosecond component assigned to the flattening of the D(2d) coordination geometry in the MLCT excited state was again present in the latter because the absence of a tert-butyl on the phenanthroline allows flattening to the pseudotetrahedral coordination geometry. Unlike the [Cu(I)(dtbp)(2)](+), [Cu(I)(tbp)(2)](+) exhibited no detectable emission at room temperature in solution. These results provide new insights into the manipulation of various excited state properties in Cu diimine complexes by certain key structural factors, enabling optimization of these systems for solar energy conversion applications.

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Structural forms in complexes of 2,9-dimethyl-1,10-phenanthroline with simple salts of copper(I) and other univalent ‘closed shell’ species

Cited by 11 publications

References 27 publications

Wide-Bite-Angle Diphosphine Ligands in Thermally Activated Delayed Fluorescent Copper(I) Complexes: Impact on the Performance of Electroluminescence Applications

Wide-Bite-Angle Diphosphine Ligands in Thermally Activated Delayed Fluorescent Copper(I) Complexes: Impact on the Performance of Electroluminescence Applications

Effects of Electronic and Nuclear Interactions on the Excited-State Properties and Structural Dynamics of Copper(I) Diimine Complexes

Strong Steric Hindrance Effect on Excited State Structural Dynamics of Cu(I) Diimine Complexes

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