The CO releasing ability of the complex [CpMo(CO)₃Me] (1) (Cp = η⁵-C₅H₅) has been assessed using a deoxymyoglobin-carbonmonoxymyoglobin assay. In the dark, CO release was shown to be promoted by the reducing agent sodium dithionite in a concentration-dependent manner. At lower dithionite concentrations, where dithionite-induced CO release was minimised, irradiation at 365 nm with a low-power UV lamp resulted in a strongly enhanced release of CO (half-life (t_1/2) = 6.3 min), thus establishing complex 1 as a photochemically activated CO-releasing molecule. To modify the CO release behaviour of the tricarbonyl complex, the possibility of obtaining inclusion complexes between 1 and β-cyclodextrin (βCD) or cucurbit[7]uril (CB7) by liquid–liquid interfacial precipitation (1@βCD(IP)), liquid antisolvent precipitation (1@CB7), and mechanochemical ball-milling (1@βCD(BM)) was evaluated. All these methods led to the isolation of a true inclusion compound (albeit mixed with nonincluded 1 for 1@βCD(BM)), as evidenced by powder X-ray diffraction (PXRD), thermogravimetric analysis (TGA), FT-IR and FT-Raman spectroscopies, and ¹³C{¹H} magic angle spinning (MAS) NMR. PXRD showed that 1@βCD(IP) was microcrystalline with a channel-type crystal packing structure. High resolution mass spectrometry studies revealed the formation of aqueous phase 1 : 1 complexes between 1 and CB7. For 1@βCD(IP) and 1@CB7, the protective effects of the hosts led to a decrease in the CO release rates with respect to nonincluded 1. βCD had the strongest effect, with a ca. 10-fold increase in t_1/4 for dithionite-induced CO release, and a ca. 2-fold increase in t_1/2 for photoinduced CO release.

中文翻译：

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β-环糊精和葫芦[7]脲作为一氧化碳释放分子[CpMo（CO）3Me]的保护性包封剂


已使用脱氧肌红蛋白-碳一氧肌红蛋白测定评估了复合物 [CpMo（CO）₃Me] （1） （Cp = η^5-C ₅H₅） 的 CO 释放能力。在黑暗中，还原剂连二亚硫酸钠以浓度依赖性方式促进 CO 释放。在较低的连二亚硫酸盐浓度下，连二亚硫酸盐诱导的 CO 释放最小，用低功率紫外灯在 365 nm 处照射导致 CO 的释放强烈增强（半衰期 （t_1/2） = 6.3 min），从而将复合物 1 建立为光化学激活的 CO 释放分子。为了改变三羰基络合物的 CO 释放行为，评估了通过液-液界面沉淀 （1@βCD（IP））、液体反溶剂沉淀 （1@CB7） 和机械化学球磨 （1@βCD（BM）） 获得 1 和 β-环糊精 （βCD） 或葫芦[7]uril （CB7） 之间的包合物的可能性。粉末 X 射线衍射 （PXRD）、热重分析 （TGA）、FT-IR 和 FT-拉曼光谱以及 ¹³C{¹H} 魔角旋转 （MAS） NMR 证明了这一点，所有这些方法都导致了真正的包涵物的分离（尽管与非内含物 1 对 1@βCD （BM）] 混合。PXRD 显示 1@βCD（IP） 是微晶，具有通道型晶体填充结构。高分辨率质谱研究揭示了在 1 和 CB7 之间形成 1 ： 1 水相复合物。 对于 1@βCD（IP） 和 1@CB7，宿主的保护作用导致相对于非包涵体 1 的 CO 释放速率降低。βCD 的效果最强，连二亚硫酸盐诱导的 CO 释放的 t_1/4 增加了约 10 倍，光诱导 CO 释放的 t_1/2 增加了约 2 倍。