Meyer Marco, Mardegan Lorenzo, Tordera Daniel, Prescimone Alessandro, Sessolo Michele, Bolink Henk J, Constable Edwin C, Housecroft Catherine E
Department of Chemistry, University of Basel, Mattenstrasse 24a, BPR 1096, 4058 Basel, Switzerland.
Instituto de Ciencia Molecular (ICMol), Universidad de Valencia, Catedrático José Beltrán 2, 46980 Paterna, Spain.
Dalton Trans. 2021 Dec 14;50(48):17920-17934. doi: 10.1039/d1dt03239a.
The syntheses and characterisations of a series of heteroleptic copper(I) compounds [Cu(POP)(Mebpy)][A], [Cu(POP)(Mebpy)][A], [Cu(xantphos)(Mebpy)][A] and [Cu(xantphos)(Mebpy)][A] in which [A] is [BF], [PF], [BPh] and [BAr] (Mebpy = 6-methyl-2,2'-bipyridine, Mebpy = 6,6'-dimethyl-2,2'-bipyridine, POP = oxydi(2,1-phenylene)bis(diphenylphosphane), xantphos = (9,9-dimethyl-9-xanthene-4,5-diyl)bis(diphenylphosphane), [BAr] = tetrakis(3,5-bis(trifluoromethyl)phenyl)borate) are reported. Nine of the compounds have been characterised by single crystal X-ray crystallography, and the consequences of the different anions on the packing interactions in the solid state are discussed. The effects of the counterion on the photophysical properties of [Cu(POP)(N^N)][A] and [Cu(xantphos)(N^N)][A] (N^N = Mebpy and Mebpy) have been investigated. In the solid-state emission spectra, the highest energy emission maxima are for [Cu(xantphos)(Mebpy)][BPh] and [Cu(xantphos)(Mebpy)][BPh] (emmax = 520 nm) whereas the lowest energy emmax values occur for [Cu(POP)(Mebpy)][PF] and [Cu(POP)(Mebpy)][BPh] (565 nm and 563 nm, respectively). Photoluminescence quantum yields (PLQYs) are noticeably affected by the counterion; in the [Cu(xantphos)(Mebpy)][A] series, solid-state PLQY values decrease from 62% for [PF], to 44%, 35% and 27% for [BF], [BPh] and [BAr], respectively. This latter series of compounds was used as active electroluminescent materials on light-emitting electrochemical cells (LECs). The luminophores were mixed with ionic liquids (ILs) [EMIM][A] ([EMIM] = [1-ethyl-3-methylimidazolium]) containing the same or different counterions than the copper(I) complex. LECs containing [Cu(xantphos)(Mebpy)][BPh] and [Cu(xantphos)(Mebpy)][BAr] failed to turn on under the LEC operating conditions, whereas those with the smaller [PF] or [BF] counterions had rapid turn-on times and exhibited maximum luminances of 173 and 137 cd m and current efficiencies of 3.5 and 2.6 cd A, respectively, when the IL contained the same counterion as the luminophore. Mixing the counterions ([PF] and [BF]) of the active complex and the IL led to a reduction in all the figures of merit of the LECs.
报道了一系列异配位铜（I）化合物[Cu(POP)(Mebpy)][A]、[Cu(POP)(Mebpy)][A]、[Cu(xantphos)(Mebpy)][A]和[Cu(xantphos)(Mebpy)][A]的合成与表征，其中[A]为[BF]、[PF]、[BPh]和[BAr]（Mebpy = 6 - 甲基 - 2,2'-联吡啶，Mebpy = 6,6'-二甲基 - 2,2'-联吡啶，POP = 氧二（2,1 - 亚苯基）双（二苯基膦），xantphos = （9,9 - 二甲基 - 9 - 呫吨 - 4,5 - 二基）双（二苯基膦），[BAr] = 四（3,5 - 双（三氟甲基）苯基）硼酸盐）。已通过单晶X射线晶体学对其中九种化合物进行了表征，并讨论了不同阴离子对固态堆积相互作用的影响。研究了抗衡离子对[Cu(POP)(N^N)][A]和[Cu(xantphos)(N^N)][A]（N^N = Mebpy和Mebpy）光物理性质的影响。在固态发射光谱中，能量最高的发射最大值出现在[Cu(xantphos)(Mebpy)][BPh]和[Cu(xantphos)(Mebpy)][BPh]（emmax = 520 nm），而能量最低的emmax值出现在[Cu(POP)(Mebpy)][PF]和[Cu(POP)(Mebpy)][BPh]（分别为565 nm和563 nm）。光致发光量子产率（PLQYs）明显受抗衡离子影响；在[Cu(xantphos)(Mebpy)][A]系列中，固态PLQY值从[PF]的62%分别降至[BF]、[BPh]和[BAr]的44%、35%和27%。后一系列化合物被用作发光电化学电池（LECs）的活性电致发光材料。发光体与含有与铜（I）配合物相同或不同抗衡离子的离子液体（ILs）[EMIM][A]（[EMIM] = [1 - 乙基 - 3 - 甲基咪唑鎓]）混合。含有[Cu(xantphos)(Mebpy)][BPh]和[Cu(xantphos)(Mebpy)][BAr]的LECs在LEC操作条件下无法开启，而当IL含有与发光体相同的抗衡离子时，含有较小[PF]或[BF]抗衡离子的LECs具有快速开启时间，分别表现出173和137 cd m的最大亮度以及3.5和2.6 cd A的电流效率。将活性配合物和IL的抗衡离子（[PF]和[BF]）混合会导致LECs的所有性能指标下降。
