Journal
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 56, Issue 46, Pages 14612-14617Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.201709156
Keywords
helicates; heterometallic complexes; keystone mechanism; kinetics; molecular upconversion
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Funding
- Swiss National Science Foundation
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The kinetic lability of hexadentate gallium-based tripods is sufficient to ensure thermodynamic self-assembly of luminescent heterodimetallic [GaLn(L3)(3)](6+) helicates on the hour time scale, where Ln is a trivalent 4f-block cation. The inertness is, however, large enough for preserving the triple-helical structure when [GaLn(L3)(3)](6+) is exposed to lanthanide exchange. The connection of a second gallium-based tripod further slows down the exchange processes to such an extent that spectroscopically active [CrErCr(L4)(3)](9+) can be diluted into closed-shell [GaYGa(L4)(3)](9+) matrices without metal scrambling. This feature is exploited for pushing molecular-based energy-transfer upconversion (ETU) at room temperature.
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