Knedel Tim-Oliver, Buss Stefan, Maisuls Iván, Daniliuc Constantin G, Schlüsener Carsten, Brandt Philipp, Weingart Oliver, Vollrath Annette, Janiak Christoph, Strassert Cristian A
Institut für Anorganische Chemie und Strukturchemie, Heinrich-Heine-Universität Düsseldorf, Universitätsstraße 1, 40225 Düsseldorf, Germany.
CiMIC, SoN, Institut für Anorganische und Analytische Chemie, Westfälische Wilhelms-Universität Münster, Corrensstraße 28/30, 48149 Münster, Germany.
Inorg Chem. 2020 May 18;59(10):7252-7264. doi: 10.1021/acs.inorgchem.0c00678. Epub 2020 May 7.
In this work, we synthesized two tailored phosphorescent Pt(II) complexes bearing a cyclometalating tridentate thiazole-based C^N*N pincer luminophore () and exchangeable chlorido () or cyanido () coligands. While both complexes showed photoluminescence from metal-perturbed ligand-centered triplet states (MP-LC), reached the highest phosphorescence quantum yields and displayed a significant sensitivity toward quenching by O. We encapsulated them into two Zn-based metal-organic frameworks, namely, and . The incorporation of the organometallic compounds in the resulting composites , , , and was verified by powder X-ray diffractometry, scanning electron microscopy, time-resolved photoluminescence spectroscopy and microscopy, as well as N- and Ar-gas sorption studies. The amount of encapsulated complex was determined by graphite furnace atomic absorption spectroscopy, showing a maximum loading of 3.7 wt %. If compared with their solid state forms, the solid-solution composites showed prolonged O-sensitive excited state lifetimes for the complexes at room temperature, reaching up to 18.4 μs under an Ar atmosphere, which is comparable with the behavior of the complex in liquid solutions or even frozen glassy matrices at 77 K.
在本工作中，我们合成了两种定制的磷光铂（II）配合物，它们带有一个环金属化的三齿噻唑基C^N*N钳形发光体（）以及可交换的氯（）或氰基（）共配体。虽然两种配合物均表现出源于金属扰动的配体中心三重态（MP-LC）的光致发光，但达到了最高的磷光量子产率，并且对O猝灭表现出显著的敏感性。我们将它们封装到两种锌基金属有机框架中，即和。通过粉末X射线衍射、扫描电子显微镜、时间分辨光致发光光谱和显微镜以及N2和Ar气吸附研究，验证了所得复合材料、、、和中有机金属化合物的掺入情况。通过石墨炉原子吸收光谱法测定了封装配合物的量，显示最大负载量为3.7 wt%。与它们的固态形式相比，固溶体复合材料在室温下显示出配合物延长的对O敏感的激发态寿命，在Ar气氛下可达18.4 μs，这与配合物在77 K的液体溶液甚至冷冻玻璃基质中的行为相当。
