Chakraborty Indranil, Carrington Samantha J, Roseman Graham, Mascharak Pradip K
Department of Chemistry and Biochemistry, University of California , Santa Cruz, California 95064, United States.
Inorg Chem. 2017 Feb 6;56(3):1534-1545. doi: 10.1021/acs.inorgchem.6b02623. Epub 2017 Jan 12.
Two manganese(I) carbonyl complexes derived from 2-(pyridyl)benzothiazole (pbt) and 1,10-phenanthroline (phen) release carbon monoxide (CO) under low-power broad-band visible-light illumination. CO photorelease from [Mn(CO)(pbt)(PTA)]CFSO (1, where PTA = 1,3,5-triaza-7-phosphaadamantane) is accompanied by an emergence of a strong fluorescence around 400 nm from almost nonfluorescent preirradiated 1. However, [Mn(CO)(phen)(PTA)]CFSO (2) showed no such phenomenon upon prolonged illumination under similar experimental conditions. The two analogous rhenium(I) complexes, namely, [Re(CO)(pbt)(PTA)]CFSO (3) and [Re(CO)(phen)(PTA)]CFSO (4), have also been synthesized and characterized to compare their photo properties with the manganese congeners. Complexes 3 and 4 exhibit moderate CO release upon irradiation with low-power UV light. All four complexes are highly soluble in anaerobic/aerobic aqueous media and are also considerably more stable when kept under dark conditions. The inherently luminescent rhenium complex 3 was utilized to demonstrate cellular internalization of these types of compounds by MDA-MB-231 (human breast cancer) cells, while the two biocompatible manganese(I) complexes (1 and 2) have been applied to assess the cell viability of these malignant cells upon CO delivery.
两种由2-(吡啶基)苯并噻唑(pbt)和1,10-菲咯啉(phen)衍生的锰(I)羰基配合物在低功率宽带可见光照射下会释放一氧化碳(CO)。[Mn(CO)(pbt)(PTA)]CFSO(1,其中PTA = 1,3,5-三氮杂-7-磷杂金刚烷)光释放CO的过程中,几乎无荧光的预辐照1会在400 nm左右出现强烈荧光。然而,在类似实验条件下长时间光照时,[Mn(CO)(phen)(PTA)]CFSO(2)并未出现这种现象。还合成并表征了两种类似的铼(I)配合物,即[Re(CO)(pbt)(PTA)]CFSO(3)和[Re(CO)(phen)(PTA)]CFSO(4),以比较它们与锰同系物的光性质。配合物3和4在低功率紫外光照射下表现出适度的CO释放。所有四种配合物在厌氧/好氧水性介质中都高度可溶,并且在黑暗条件下保存时也相当稳定。具有固有发光性的铼配合物3被用于证明MDA-MB-231(人乳腺癌)细胞对这类化合物的细胞内化作用,而两种生物相容性锰(I)配合物(1和2)已被用于评估在递送CO时这些恶性细胞的细胞活力。