American Chemical Society
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Boron-Dipyrromethene-Functionalized Hemilabile Ligands as “Turn-On” Fluorescent Probes for Coordination Changes in Weak-Link Approach Complexes

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journal contribution
posted on 2013-05-06, 00:00 authored by Alejo M. Lifschitz, Chad M. Shade, Alexander M. Spokoyny, Jose Mendez-Arroyo, Charlotte L. Stern, Amy A. Sarjeant, Chad A. Mirkin
Herein we report a new class of hemilabile ligands with boron-dipyrromethene (Bodipy) fluorophores that, when complexed to Pt­(II), can signal changes in coordination mode through changes in their fluorescence. The ligands consist of phosphino-amine or phosphino-thioether coordinating moieties linked to the Bodipy’s meso carbon via a phenylene spacer. Interestingly, this new class of ligands can be used to signal both ligand displacement and chelation reactions in a fluorescence “turn-on” fashion through the choice of weakly binding heteroatom in the hemilabile moiety, generating up to 10-fold fluorescence intensity increases. The Pt­(II) center influences the Bodipy emission efficiency by regulating photoinduced electron transfer between the fluorophore and its meso substituent. The rates at which the excited Bodipy-species generate singlet oxygen upon excitation suggest that the heavy Pt­(II) center also influences Bodipy’s emission efficiency by affecting intersystem crossing from the Bodipy excited singlet to excited triplet states. This signaling strategy provides a quantitative read-out for changes in coordination mode and potentially will enable the design of new molecular systems for sensing and signal amplification.