Metallacycle-cored supramolecular assemblies with tunable fluorescence including white-light emission
- 6 March 2017
- journal article
- Published by Proceedings of the National Academy of Sciences in Proceedings of the National Academy of Sciences of the United States of America
- Vol. 114 (12), 3044-3049
- https://doi.org/10.1073/pnas.1702510114
Abstract
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., 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.Keywords
Funding Information
- National Science Foundation (NSF) (1212799)
- National Natural Science Foundation of China (NSFC) (21574034)
- National Natural Science Foundation of China (NSFC) (21274034)
- Zhejiang Province Natural Science Foundation of China (LY16B040006)
This publication has 48 references indexed in Scilit:
- Recent progress in the design and applications of fluorescence probes containing crown ethersChemical Society Reviews, 2016
- Nanoparticles with Near-Infrared Emission Enhanced by Pillararene-Based Molecular Recognition in WaterJournal of the American Chemical Society, 2015
- Supramolecular biomaterialsNature Materials, 2015
- Biological Applications of Supramolecular Assemblies Designed for Excitation Energy TransferChemical Reviews, 2015
- Recent Advances in Supramolecular Analytical Chemistry Using Optical SensingChemical Reviews, 2015
- Current developments in fluorescent PET (photoinduced electron transfer) sensors and switchesChemical Society Reviews, 2015
- Biomedical Applications of Supramolecular Systems Based on Host–Guest InteractionsChemical Reviews, 2014
- Small molecule-based ratiometric fluorescence probes for cations, anions, and biomoleculesChemical Society Reviews, 2014
- Fluorescent Dyes and Their Supramolecular Host/Guest Complexes with Macrocycles in Aqueous SolutionChemical Reviews, 2011
- Molecular Wire Encapsulated into π Organogels: Efficient Supramolecular Light‐Harvesting Antennae with Color‐Tunable EmissionAngewandte Chemie-International Edition, 2007