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Shine bright or live long: substituent effects in [Cu(N^N)(P^P)]+-based light-emitting electrochemical cells where N^N is a 6-substituted 2,2'-bipyridine

Keller, S. and Pertegás, A. and Longo, G. and Martínez, L. and Cerdá, J. and Junquera-Hernández, J. M. and Prescimone, A. and Constable, E. C. and Housecroft, C. E. and Ortí, E. and Bolink, H. J.. (2016) Shine bright or live long: substituent effects in [Cu(N^N)(P^P)]+-based light-emitting electrochemical cells where N^N is a 6-substituted 2,2'-bipyridine. Journal of materials chemistry C, 4 (17). pp. 3857-3871.

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Abstract

We report [Cu(P^P)(N^N)][PF6] complexes with P^P = bis(2-(diphenylphosphino)phenyl)ether (POP) or 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (xantphos) and N^N = 6-methyl-2,2′-bipyridine (Mebpy), 6-ethyl-2,2′-bipyridine (Etbpy), 6,6′-dimethyl-2,2′-bipyridine (Me2bpy) or 6-phenyl-2,2′-bipyridine (Phbpy). The crystal structures of [Cu(POP)(Phbpy)][PF6]·Et2O, [Cu(POP)(Etbpy)][PF6]·Et2O, [Cu(xantphos)(Me2bpy)][PF6], [Cu(xantphos)(Mebpy)][PF6]·CH2Cl2·0.4Et2O, [Cu(xantphos)(Etbpy)][PF6]·CH2Cl2·1.5H2O and [Cu(xantphos)(Phbpy)][PF6] are described; each copper(I) centre is distorted tetrahedral. In the crystallographically determined structures, the N^N domain in [Cu(xantphos)(Phbpy)]+ and [Cu(POP)(Phbpy)]+ is rotated ∼180° with respect to its orientation in [Cu(xantphos)(Mebpy)]+, [Cu(POP)(Etbpy)]+ and [Cu(xantphos)(Etbpy)]+; in each complex containing xantphos, the xanthene ‘bowl’ retains the same conformation in the solid-state structures. The two conformers resulting from the 180° rotation of the N^N ligand were optimized at the B3LYP-D3/(6-31G**+LANL2DZ) level and are close in energy for each complex. Variable temperature NMR spectroscopy evidences the presence of two conformers of [Cu(xantphos)(Phbpy)]+ in solution which are related by inversion of the xanthene unit. The complexes exhibit MLCT absorption bands in the range 378 to 388 nm, and excitation into each MLCT band leads to yellow emissions. Photoluminescence quantum yields (PLQYs) increase from solution to thin-film and powder; the highest PLQYs are observed for powdered [Cu(xantphos)(Mebpy)][PF6] (34%), [Cu(xantphos)(Etbpy)][PF6] (37%) and [Cu(xantphos)(Me2bpy)][PF6] (37%) with lifetimes of 9.6–11 μs. Density functional theory calculations predict that the emitting triplet (T1) involves an electron transfer from the Cu–P^P environment to the N^N ligand and therefore shows a 3MLCT character. T1 is calculated to be ∼0.20 eV lower in energy than the first singlet excited state (S1). The [Cu(P^P)(N^N)][PF6] ionic transition-metal (iTMC) complexes were tested in light-emitting electrochemical cells (LECs). Turn-on times are fast, and the LEC with [Cu(xantphos)(Me2bpy)][PF6] achieves a maximum efficacy of 3.0 cd A−1 (luminance = 145 cd m−2) with a lifetime of 1 h; on going to the [Cu(xantphos)(Mebpy)][PF6]-based LEC, the lifetime exceeds 15 h but at the expense of the efficacy (1.9 cd A−1). The lifetimes of LECs containing [Cu(xantphos)(Etbpy)][PF6] and [Cu(POP)(Etbpy)][PF6] exceed 40 and 80 h respectively.
Faculties and Departments:05 Faculty of Science > Departement Chemie > Chemie > Anorganische Chemie (Constable)
05 Faculty of Science > Departement Chemie > Chemie > Anorganische Chemie (Housecroft)
UniBasel Contributors:Housecroft, Catherine Elizabeth and Constable, Edwin Charles and Keller, Sarah and Prescimone, Alessandro
Item Type:Article, refereed
Publisher:Royal Society of Chemistry
ISSN:2050-7534
Note:Publication type according to Uni Basel Research Database: Journal article
Language:English
Identification Number:
Last Modified:30 Jun 2016 11:03
Deposited On:26 May 2016 10:23

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