Fluorescent metallosupramolecules
have received considerable attention
due to their precisely controlled dimensions as well as the tunable
photophysical and photochemical properties. However, phosphorescent
analogues are still rare and limited to small structures with low-temperature
phosphorescence. Herein, we report the self-assembly and photophysical
studies of a giant, discrete metallosupramolecular concentric hexagon
functionalized with six alkynylplatinum(II) bzimpy moieties. With
a size larger than 10 nm and molecular weight higher than 26 000
Da, the assembled terpyridine-based supramolecule displayed phosphorescent
emission at room temperature. Moreover, the supramolecule exhibited
enhanced aggregation-induced phosphorescent emission compared to the
ligand by tuning the aggregation states through intermolecular interactions
and significant enhancement of emission to CO2 gas.
Summary of main observation and conclusion
Porphyrins have been widely used in the self‐assembly of metallo‐supramolecules. In this study, we introduced 2,2':6,2"‐terpyridine (tpy) into a porphyrin core to synthesize a tetratopic building block with multiple conformers. During the self‐assembly with Zn(II), such a mixture of conformers was able to form a discrete nanoprism with all building blocks in one conformation. Detailed characterizations, including NMR, ESI‐MS and traveling‐wave ion mobility‐mass spectrometry (TWIM‐MS), all supported the formation of the desired assemblies. AFM and TEM further confirmed the dimensions of assembled nanoprisms. Moreover, the photophysical properties of the ligands and complexes were noticeably different depending upon size and metal ion center.
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