title: Peripheral halo-functionalization in [Cu(N^N)(P^P)]+emitters: influence on the performances of light-emitting electrochemical cells.
abstract: A series of heteroleptic [Cu(N^N)(P^P)][PF6] complexes is described in which P^P = bis(2-(diphenylphosphino)phenyl)ether (POP) or 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (xantphos) and N^N = 4,4'-diphenyl-6,6'-dimethyl-2,2'-bipyridine substituted in the 4-position of the phenyl groups with atom X (N^N = 1 has X = F, 2 has X = Cl, 3 has X = Br, 4 has X = I; the benchmark N^N ligand with X = H is 5). These complexes have been characterized by multinuclear NMR spectroscopy, mass spectrometry, elemental analyses and cyclic voltammetry; representative single crystal structures are also reported. The solution absorption spectra are characterized by high energy bands (arising from ligand-centred transitions) which are red-shifted on going from X = H to X = I, and a broad metal-to-ligand charge transfer band with λmaxin the range 387-395 nm. The ten complexes are yellow emitters in solution and yellow or yellow-orange emitters in the solid-state. For a given N^N ligand, the solution photoluminescence (PL) spectra show no significant change on going from [Cu(N^N)(POP)]+to [Cu(N^N)(xantphos)]+; introducing the iodo-functionality into the N^N domain leads to a red-shift in λ compared to the complexes with the benchmark N^N ligand 5. In the solid state, [Cu(1)(POP)][PF6] and [Cu(1)(xantphos)][PF6] (fluoro-substituent) exhibit the highest PL quantum yields (74 and 25%, respectively) with values of τ1/2= 11.1 and 5.8 μs, respectively. Light-emitting electrochemical cells (LECs) with [Cu(N^N)(P^P)][PF6] complexes in the emissive layer have been tested. Using a block-wave pulsed current driving mode, the best performing device employed [Cu(1)(xantphos)]+and this showed a maximum luminance (Lummax) of 129 cd m-2and a device lifetime (t1/2) of 54 h; however, the turn-on time (time to reach Lummax) was 4.1 h. Trends in performance data reveal that the introduction of fluoro-groups is beneficial, but that the incorporation of heavier halo-substituents leads to poor devices, probably due to a detrimental effect on charge transport; LECs with the iodo-functionalized N^N ligand 4 failed to show any electroluminescence after 50 h.
authors.affiliation: Department of Chemistry, University of Basel, Spitalstrasse 51, CH-4056 Basel, Switzerland. catherine.housecroft@unibas.ch.
authors.forename: Fabian
authors.initials: F
authors.lastname: Brunner
authors.affiliation: Instituto de Ciencia Molecular, Universidad de Valencia, Catedrático José Beltrán 2, Paterna, E-46980, Spain. henk.bolink@uv.es.
authors.forename: Laura
authors.initials: L
authors.lastname: Martínez-Sarti
authors.affiliation: Department of Chemistry, University of Basel, Spitalstrasse 51, CH-4056 Basel, Switzerland. catherine.housecroft@unibas.ch.
authors.forename: Sarah
authors.initials: S
authors.lastname: Keller
authors.affiliation: Instituto de Ciencia Molecular, Universidad de Valencia, Catedrático José Beltrán 2, Paterna, E-46980, Spain. henk.bolink@uv.es.
authors.forename: Antonio
authors.initials: A
authors.lastname: Pertegás
authors.affiliation: Department of Chemistry, University of Basel, Spitalstrasse 51, CH-4056 Basel, Switzerland. catherine.housecroft@unibas.ch.
authors.forename: Alessandro
authors.initials: A
authors.lastname: Prescimone
authors.affiliation: Department of Chemistry, University of Basel, Spitalstrasse 51, CH-4056 Basel, Switzerland. catherine.housecroft@unibas.ch.
authors.forename: Edwin C
authors.initials: EC
authors.lastname: Constable
authors.affiliation: Instituto de Ciencia Molecular, Universidad de Valencia, Catedrático José Beltrán 2, Paterna, E-46980, Spain. henk.bolink@uv.es and Fundació General de la Universitat de Valencia (FGUV), PO Box 22085, Valencia, Spain.
authors.forename: Henk J
authors.initials: HJ
authors.lastname: Bolink
authors.affiliation: Department of Chemistry, University of Basel, Spitalstrasse 51, CH-4056 Basel, Switzerland. catherine.housecroft@unibas.ch.
authors.forename: Catherine E
authors.initials: CE
authors.lastname: Housecroft