Carrasco Irene, Ehni Philipp, Ebert Max, Dumait Noée, Taupier Gregory, Amela-Cortes Maria, Roiland Claire, Cordier Stéphane, Knöller Julius A, Jacques Emmanuel, Laschat Sabine, Molard Yann
Univ Rennes, CNRS, ISCR─UMR 6226, ScanMAT─UAR 2025, IETR─UMR6164, F-35000 Rennes, France.
Institut für Organische Chemie, Universität Stuttgart, Pfaffenwaldring 55, 70569 Stuttgart, Germany.
ACS Appl Mater Interfaces. 2023 Aug 23;15(33):39752-39764. doi: 10.1021/acsami.3c08441. Epub 2023 Aug 11.
Molecular or supramolecular materials that can self-organize into columns such as discotic liquid crystals are of interest for several applications in the field of optoelectronics. We show in this work that red near-infrared (NIR)-emissive metal cluster compounds of general formula NaMoXCl (X = Cl or Br) can be readily complexed with discotic liquid crystals containing a crown ether. Three cavity sizes have been tested with crown ethers bearing 4, 5, or 6 oxygen atoms. In all cases, 1:1 complexes were formed, thanks to the well-known supramolecular interactions existing between the Na cations of the metal cluster salt and the crown ether derivatives. All obtained hybrids are homogeneous, emit in the red NIR region, and show liquid crystalline properties on a wider temperature range than their precursors. Charge transport properties have been investigated by using a space charge limited current device. Obtained results demonstrate that metal cluster compounds can enhance the charge carrier mobility by 5 orders of magnitude compared to the native discotic organic ligands. Considering that the presented organic crown ether derivatives are not the best candidates to design optoelectronic devices because of their inherently low conductivity, but that similar compounds were developed to design proton conductive porous framework, our results open promising perspectives for the use of metal cluster compounds in devices dedicated to such a field.
能够自组装成柱状结构的分子或超分子材料,如盘状液晶,在光电子学领域有多种应用。我们在这项工作中表明,通式为NaMoXCl(X = Cl或Br)的红色近红外(NIR)发光金属簇化合物能够很容易地与含有冠醚的盘状液晶形成络合物。我们测试了含有4个、5个或6个氧原子的冠醚的三种空腔尺寸。在所有情况下,由于金属簇盐中的Na阳离子与冠醚衍生物之间存在众所周知的超分子相互作用,均形成了1:1的络合物。所有得到的杂化物都是均匀的,在红色近红外区域发光,并且在比其前体更宽的温度范围内表现出液晶性质。我们使用空间电荷限制电流装置研究了电荷传输性质。所得结果表明,与天然盘状有机配体相比,金属簇化合物可将电荷载流子迁移率提高5个数量级。鉴于所呈现的有机冠醚衍生物因其固有低导电性并非设计光电器件的最佳候选物,但已开发出类似化合物用于设计质子传导多孔骨架,我们的结果为金属簇化合物在致力于该领域的器件中的应用开辟了广阔前景。