期刊名称：Proceedings of the National Academy of Sciences
印刷版ISSN：0027-8424
电子版ISSN：1091-6490
出版年度：2017
卷号：114
期号：12
页码：3044-3049
DOI：10.1073/pnas.1702510114
语种：English
出版社：The National Academy of Sciences of the United States of America
摘要：Control over the fluorescence of supramolecular assemblies is crucial for the development of chemosensors and light-emitting materials. Consequently, the postsynthetic modification of supramolecular structures via host–guest interactions has emerged as an efficient strategy in recent years that allows the facile tuning of the photophysical properties without requiring a tedious chemical synthesis. Herein, we used a phenanthrene-21-crown-7 (P21C7)-based 60° diplatinum(II) acceptor 8 in the construction of three exohedral P21C7 functionalized rhomboidal metallacycles 1–3 which display orange, cyan, and green emission colors, respectively. Although these colors originate from the dipyridyl precursors 10–12, containing triphenylamine-, tetraphenylethene-, and pyrene-based fluorophores, respectively, the metal–ligand coordination strongly influences their emission properties. The metallacycles were further linked into emissive supramolecular oligomers by the addition of a fluorescent bis-ammonium linker 4 that forms complementary host–guest interactions with the pendant P21C7 units. Notably, the final ensemble derived from a 1:1 mixture of 1 and 4 displays a concentration-dependent emission. At low concentration, i.e., <25 µM, it emits a blue color, whereas an orange emission was observed when the concentration exceeds >5 mM. Moreover, white-light emission was observed from the same sample at a concentration of 29 µM, representing a pathway to construct supramolecular assemblies with tunable fluorescence properties.
