“…However, halide-to-ligand charge-transfer ( 3 XLCT) or ligand-to-ligand charge-transfer ( 3 LLCT) may also occur, as well as mixing with intraligand 3 IL (π → π * ) states [20,26,27]. Although the nature of their emission is thus phosphorescence, these complexes are widely referred to as luminescent in the literature, and we will use this terminology in the following.…”
Section: Spectroscopic Properties Of Luminescent Re(i) Tricarbonyl Comentioning
Bio-imaging, by enabling the visualization of biomolecules of interest, has proved to be highly informative in the study of biological processes. Although fluorescence microscopy is probably one of the most used techniques, alternative methods of imaging, providing complementary information, are emerging. In this context, metal complexes represent valuable platforms for multimodal imaging, since they may combine interesting spectroscopic features and biologically relevant functionalization on a single molecular core. In particular, d6 low-spin rhenium tri-carbonyl complexes display unique luminescence and vibrational properties, and can be readily functionalized. Here we review their applications and potential as probes or drugs relying on their photophysical properties, before focusing on their use as multimodal probes for the labelling and imaging of peptides and proteins.
“…However, halide-to-ligand charge-transfer ( 3 XLCT) or ligand-to-ligand charge-transfer ( 3 LLCT) may also occur, as well as mixing with intraligand 3 IL (π → π * ) states [20,26,27]. Although the nature of their emission is thus phosphorescence, these complexes are widely referred to as luminescent in the literature, and we will use this terminology in the following.…”
Section: Spectroscopic Properties Of Luminescent Re(i) Tricarbonyl Comentioning
Bio-imaging, by enabling the visualization of biomolecules of interest, has proved to be highly informative in the study of biological processes. Although fluorescence microscopy is probably one of the most used techniques, alternative methods of imaging, providing complementary information, are emerging. In this context, metal complexes represent valuable platforms for multimodal imaging, since they may combine interesting spectroscopic features and biologically relevant functionalization on a single molecular core. In particular, d6 low-spin rhenium tri-carbonyl complexes display unique luminescence and vibrational properties, and can be readily functionalized. Here we review their applications and potential as probes or drugs relying on their photophysical properties, before focusing on their use as multimodal probes for the labelling and imaging of peptides and proteins.
“…5 These CO complexes are often desirable for their facile synthesis, superior stability in various organic media, and strong luminescence. 6–8 The convenient syntheses of [Re(CO) 3 X(L)] type complexes (where L = α -diimine ligand and X = monodentate ancillary ligand) and amenability of the α -diimine ligands toward various derivatization enable systematic tuning of the electronic properties of these complexes. 9,10 Recently, the vast literature on these organometallic systems and their rich photochemistry have encouraged us to design and synthesize new rhenium carbonyl-based photoactive CO-releasing materials (photoCORMs) for site-specific delivery of CO to biological targets.…”
A family of Re(I) carbonyl complexes of general formula [ReX(CO)3(phen)]0/1+ (where X = Cl−, CF3SO3−, MeCN, PPh3, and methylimidazole) derived from 1,10-phenanthroline (phen) exhibits variable emission characteristics depending on the presence of the sixth ancillary ligand/group (X). All complexes but with X = MeCN exhibit moderate CO release upon irradiation with low-power UV light and are indefinitely stable in anaerobic/aerobic environment in solution as well as in solid state when kept under dark condition. These CO donors liberate three, one, or no CO depending on the nature of sixth ligand upon illumination as studied with the aid of time-dependent IR spectroscopy. Results of excited-state density functional theory (DFT) and time-dependent DFT calculations provided insight into the origin of the emission characteristics of these complexes. The luminescent rheinum(I) photoCORMs uniformly displayed efficient cellular internalization by the human breast adenocarcinoma cells, MDA-MB-231, while the complex with PPh3 as ancillary ligand showed moderate nuclear localization in addition to the cytosolic distribution. These species hold significant promise as theranostic photoCORMs (photoinduced CO releasing molecules), where the entry of the pro-drug can be tracked within the cellular matrices.
“…4). We have assigned this emission to a triplet metal-to-ligand charge-transfer ( 3 MLCT) (dS(Re) o S*(Me 2 bpy)) state [5] [13]. To study the potential use of the fluorous label in biological enrichment and purification applications, the bioconjugate Re-GSH in a mixture of twenty amino acids has been isolated and purified using an FSPE column.…”
Section: Resultsmentioning
confidence: 99%
“…Previously, we have reported luminescent transition metal polypyridine complexes as biological labeling reagents [5] [7] and noncovalent probes for biomolecules and ions [8] [11]. In view of the rich photophysical properties of rhenium(I) polypyridine complexes [5] [13], we anticipate that a new luminescent fluorous labeling reagent can be achieved by functionalizing a luminescent rhenium(I) polypyridine complex with an amine-specific isothiocyanate group and a fluorous pendant.…”
We present the synthesis and characterization of luminescent biological probes derived from rhenium(I) polypyridine fluorous complexes [Re(Me 2 bpy)(CO) 3 (py-Rf-R)](PF 6 ) (R = NH 2 (1), NCS (2), TU-C 2 H 5 (3)). The photophysical properties of these complexes have been studied. The fluorous complex 2 has been used to label glutathione (GSH) and bovine serum albumin (BSA). The photophysical properties of the resultant bioconjugates have been studied. The isolation of the luminescent fluorous rhenium-GSH conjugate from a mixture of twenty amino acids has been demonstrated using fluorous solidphase extraction (FSPE).Additionally, the cytotoxicity of complexes 1 and 3 toward HeLa cells has been examined by the 3-(4,5-dimethyl-2-thiazolyl)-2,5-diphenyltetrazolium bromide (MTT) assay. The cellular uptake properties of complex 3 have been investigated by laser-scanning confocal microscopy.
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