Wavelength‐Dependent Control of the CO Release Kinetics of Manganese(I) Tricarbonyl PhotoCORMs with Benzimidazole Coligands

Wavelength‐Dependent Control of the CO Release Kinetics of Manganese(I) Tricarbonyl PhotoCORMs with Benzimidazole Coligands
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苯并咪唑配体对三羰基锰 (I) PhotoCORM 的 CO 释放动力学的波长依赖性控制

DOI:
10.1002/ejic.201900894
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发表时间:
2019
影响因子:
2.3
通讯作者:
U. Schatzschneider
U. Schatzschneider
中科院分区:
化学3区
文献类型:
--
作者:
A. Mansour;C. Steiger;C. Nagel;U. Schatzschneider

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由五羰基溴化锰和带有不同给电子基团和吸电子基团 R = H、4-CH3、4-OCH3、4-Cl、4-NO2 的 1H-苯并咪唑-2-基甲基-(N-苯基)胺配体 (L) 制备了一系列光活化 CO 释放分子 (PhotoCORMs)。 2-、3-和4-COOCH3在苯基取代基上,得到通式[MnBr(CO)3(L)]的八面体锰(I)络合物。化合物的充气 DMSO 溶液在黑暗中稳定 16 小时,没有 CO 释放。然而,这些化合物在 412-525 nm 照射下会迅速释放 CO,具体取决于取代模式。使用紫外/可见光谱和商用气体传感器系统的二氧化碳释放测量,系统地探讨了它对光物理和光化学性质的影响。在硝基取代的化合物中,电子激发态从苯并咪唑中心转变为苯基中心,导致这种可见光激活的 PhotoCORM 具有明显不同的光化学行为。
A series of photoactivatable CO‐releasing molecules (PhotoCORMs) was prepared from manganese pentacarbonyl bromide and 1H‐benzimidazol‐2‐ylmethyl‐(N‐phenyl)amine ligands (L) bearing different electron‐donating and electron‐withdrawing groups R = H, 4‐CH3, 4‐OCH3, 4‐Cl, 4‐NO2, 2‐, 3‐, and 4‐COOCH3on the phenyl substituent to give octahedral manganese(I) complexes of the general formula [MnBr(CO)3(L)]. Aerated DMSO solutions of the compounds are stable in the dark for 16 h with no CO release. However, the compounds rapidly release CO upon illumination at 412–525 nm, depending on the substitution pattern. Its influence on the photophysical and photochemical properties was systematically explored using UV/Vis spectroscopy and CO release measurements with a commercial gas sensor system. In the nitro‐substituted compound, the electronically excited state switched from benzimidazole‐ to phenyl‐centered, leading to a markedly different photochemical behavior of this visible‐light activated PhotoCORM.
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