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Triazolylidene Metal Complexes Tagged with a Bodipy Chromophore: Synthesis and Monitoring of Ligand Exchange Reactions
journal contribution
posted on 2017-01-18, 17:34 authored by Miquel Navarro, Suxiao Wang, Helge Müller-Bunz, Gareth Redmond, Pau Farràs, Martin AlbrechtThe
alkyne azide “click” reaction was successfully used
to prepare new Bodipy-functionalized triazoles and triazolium salts.
The Bodipy functionality was compatible with cyclometalation conditions
as well as with transmetalation procedures involving a triazolyldene
silver intermediate, as demonstrated by the successful formation of
a metallacyclic palladium dimer and an iridium chelate. Both complexes
were characterized by X-ray diffraction, and spectroscopic studies
demonstrate unperturbed photoluminescence of the Bodipy chromophore
(emission around 545 nm, quantum yields in the 0.35–0.7 range,
and excited-state lifetimes between 3 and 7 ns). The palladium dimer 4 was cleaved using N,N-dimethylaminopyridine
(dmap) and acridine to afford monomeric triazolylidene palladium complexes 5 and 6. While dmap is a classical spectator
ligand, acridine acts as photoluminescence quencher and quenching
constants were determined as KSV = 0.86
and 1.6 × 104 M–1 for complexes 4 and 5, respectively. This dual reactivity of
acridine as ligand and quencher was utilized for a ligand displacement
assay that allowed modification of the organometallic site of the
hybrid complex to be monitored by emission spectroscopy.
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photoluminescence quencherLigand Exchange Reactionspalladium dimer 4K SVspectroscopic studiesexcited-state lifetimescyclometalation conditionsacridine actsmetallacyclic palladium dimerspectator ligand7 nsX-ray diffractiontriazolyldene silvercomplexes 4dmapquantum yieldsBodipy functionalityquenching constantsemission spectroscopyTriazolylidene Metal Complexes Taggedorganometallic siteBodipy ChromophoreBodipy chromophoreiridium chelateBodipy-functionalized triazolesligand displacement assay545 nmtransmetalation proceduresmonomeric triazolylidene palladium complexes 5triazolium salts
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