Functionalization of luminescent cyclometalated iridium(iii) polypyridine complexes with a fluorous moiety: photophysics, protein-binding, bioconjugation, and cellular uptake properties

Abstract

A new class of luminescent cyclometalated iridium(III) polypyridine fluorous complexes has been designed; the fluorous pendant not only plays an important role in the photophysical and biological properties of the complexes, but also allows the facile isolation of biomolecules labeled with these complexes with fluorous solid-phase extraction (FSPE).

Phosphorescent iridium(III)-bis-N-heterocyclic carbene complexes as mitochondria-targeted theranostic and photodynamic anticancer agents

“…S7). As iridium is an exogenous element, the cellular uptake levels of Ir(III) can be quantitatively determined by ICP-MS [39]. After incubation with 10 mM complexes for 1 h, the intracellular iridium contents of 1, 2 and 3 are in the following order: 3 (4.1 ± 0.3 pmol per cell) > 2 (2.2 ± 0.2 pmol per cell) > 1 (0.6 ± 0.1 pmol per cell).…”

“…The intracellular iridium contents of 1, 2 and 3 were determined by a method reported in literature with slight modifications [39]. Briefly, HeLa cells were grown in 60 mm tissue culture dishes and incubated for 24 h. The medium was removed and replaced with medium-DMSO (99:1 v/v) containing 1, 2 or 3 (10 mM).…”

Synthesis, Properties, and Light-Emitting Electrochemical Cell (LEEC) Device Fabrication of Cationic Ir(III) Complexes Bearing Electron-Withdrawing Groups on the Cyclometallating Ligands

“…They are therefore attractive for reducing interactions between iridium complexes, which could otherwise lead to aggregation-induced broadening and red-shifting of the phosphorescence. 43−47 This is particularly important in blue electroluminescent devices and in particular LEECs as the light-emitting layer is often a neat film. Tuning of optoelectronic properties in organometallic Ir(III) complexes using bulky fluorocarbon groups is also relatively rare compared to those with other transition metal ions.…”

“…Tuning of optoelectronic properties in organometallic Ir(III) complexes using bulky fluorocarbon groups is also relatively rare compared to those with other transition metal ions. 21,25,39,45,47−49 Thus, stable, bulky, and electron-withdrawing fluorocarbon groups are desirable alternatives to the commonly used C(aryl)–F motif and should serve the similar purpose of fine-tuning of optoelectronic properties of their Ir(III) complexes.…”

Fluorous Organometallic Chemistry

“…Bridge cleavage with pyridine or PPh 3 generates a series of mononuclear complexes (23); the complex with one C 6 F 13 unit and L¼PPh 3 (23d) has been structurally characterised. In 2011, a series of luminescent iridium(III) biscyclometalated cations [Ir(N-C) 2 (N-N)](PF 6 ) with two C 8 F 17 ponytails were reported, in which the fluorous substituents appeared to impact positively on the photophysical and biological properties [121]. The oxime-based palladacycle (24), formed in a slow reaction of the free oxime with Li 2 PdCl 4 in acetone at reflux, has been shown to be a highly effective pre-catalyst for SuzukiMiyaura, Sonagashira, Stille, Heck and Kumada reactions, either in aqueous solution or organic solvents, that could be recycled and reused up to five times [122,123].…”