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Download fileImmobilizing Tetraphenylethylene into Fused Metallacycles: Shape Effects on Fluorescence Emission
journal contribution
posted on 2016-09-27, 00:00 authored by Zhixuan Zhou, Xuzhou Yan, Manik Lal Saha, Mingming Zhang, Ming Wang, Xiaopeng Li, Peter J. StangHerein, we describe
the selective formation of a discrete fused
metallarhomboid and a triangle by the careful control of the
shape and stoichiometry of the building blocks. A tetraphenylethylene
(TPE)-based tetrapyridyl donor is exploited as the bridging component,
and coordination immobilization of the TPE unit within the rigid metallacyclic
frameworks efficiently suppresses its intramolecular rotational
motions. As a result, the fused polygons are innately emissive in
dilute solution, representing an alternative to aggregation-induced
emission. Upon further molecular aggregation, these metallacycles
display aggregation-induced enhanced emissions. Interestingly, the
fused rhomboid 7 shows a weaker fluorescence in dilute
solutions relative to that of the fused triangle 8, while
a reversal of emission intensities was observed in the aggregated
state. These markedly different fluorescence efficiencies are likely
due to the differences in the shapes of the fused polygons. Thus,
this work shows that the properties of supramolecular coordination
complexes can be affected by subtle structural factors, which can
be controlled easily and precisely at the molecular level.
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building blockssupramolecular coordination complexesaggregated statefluorescence efficienciesShape Effectspolygontriangle 8TPE unitsolutionemission intensitiescoordination immobilizationFused Metallacyclesaggregation-induced emissionmetallaImmobilizing Tetraphenylethylenerhomboid 7Fluorescence Emission Herein