Rapid CO release from a Mn(i) carbonyl complex derived from azopyridine upon exposure to visible light and its phototoxicity toward malignant cells

Abstract

Two Mn(I) carbonyl complexes namely [MnBr(azpy)(CO)3] and [Mn(azpy)(CO)3(PPh3)](ClO4) (azpy = 2-phenylazopyridine) have been synthesized and characterized. Both complexes exhibit rapid CO release upon exposure to low power visible light. [MnBr(azpy)(CO)3] shows significant phototoxicity toward two malignant cell lines HeLa and MDA-MB-231.

PhotoCORMs: CO release moves into the visible

“…65,67,75,80 Whilst these studies show that the compounds tests are not toxic, the potential of photoCORMs in active toxicity toward cancer cells has also been considered. 46,74 The latter studies focus on the possible 'turn on' of activity when irradiated.…”

“…25). 74,75 These systems offer good CO release behaviour in the visible, with fac-[Mn (38)(CO) 3 Br] showing an absorption maximum at 586 nm, and a rate for CO release of 5 min −1 when irradiated with broadband light (cutoff 520 nm). Carbon monoxide release from fac-[Mn(39)(CO) 3 Br] can be traced in vitro by fluorescence measurement and was shown to lead to cell apoptosis.…”

Self‐Assembly of Oxamidato‐Chelated ReI‐ and MnI‐Based Flexible Dinuclear Horse‐Stirrup‐Like Metallacycles

“…[32,[40][41][42][43][44][45][46] Further, a strong band in the range ν = 1596-1604 cm -1 was characteristic of the C=O stretching frequency of the bridging oxamide moiety. The shift of the oxamide C=O stretching frequency and the disappearance of the NH stretching frequency in comparison with the spectra of the free oxamide ligands indicated the chelation of the oxamide ligands between the two metal centers.…”

“…[ [40][41][42][43][44] Although a few examples of heteroligand-bridged dirhenium metallacycles are available, equivalent one-step self-assembled examples with Mn I centers are hitherto unknown. Hence, herein, we report on the one-pot self-assembly of oxamidato-bridged Mn I -and Re I -based homodimetallic metallacycles of general formula [(CO) 3 10 (M = Mn, Re), oxamide li-gands (H 2 L), and flexible exo-bidentate dipyridyl ligands (LЈ).…”

Tuning coordination modes of pyridine/thioether Schiff base (NNS) ligands to mononuclear manganese carbonyls

“…23 Related photoactive manganese(I) tricarbonyls were also derived from diazopyridine, diimine N2, and N3 ligands. [23][24][25] Most relevant to this work are complexes derived from similar Schiff base ligands with a pendant thioether-S. In the two cases of [(L NNS )-Mn(CO) 3 ] + (L = pmtpm and qmtpm; NNS and Q NNS in our nomenclature), the thioether remained unbound.…”