School of Materials Science and Engineering, Center for Supramolecular Chemistry and Catalysis and Department of Chemistry, Shanghai University, Shanghai 200444, China.
Shanghai Key Laboratory of Rare Earth Functional Materials, Department of Chemistry and Materials Science, Shanghai Normal University, Shanghai 200234, China.
J Am Chem Soc. 2022 Oct 19;144(41):18834-18843. doi: 10.1021/jacs.2c04734. Epub 2022 Oct 6.
We report a stable, water-soluble, mononuclear manganese(IV) complex [Mn(H)]·5HO (Mn-HDCL) that acts as an efficient photothermal material. This system is based on a hexahydrazide clathrochelate ligand (/HDCL) and is obtained via an efficient one-pot templated synthesis that avoids the need for harsh reaction conditions. Scanning tunneling microscopy images reveal that Mn-HDCL exists as a 2D sheet-like structure. In Mn-HDCL, the manganese(IV) ion is trapped within the cavity of the cage-like ligand. This effectively shields the Mn(IV) ion from the external environment while providing adequate water solubility. As a result of orbital transitions involving the coordinated manganese(IV) ion, as well as metal-to-ligand charge transfer effects, Mn-HDCL possesses a large extinction coefficient and displays a photothermal performance comparable to single-wall carbon nanotubes in the solid state. A high photothermal conversion efficiency (ca. 71%) was achieved in aqueous solution when subjected to near-infrared 730 nm laser photo-irradiation. Mn-HDCL is paramagnetic and provides a modest increase in the -weighted contrast of magnetic resonance images both and . Mn-HDCL was found to target tumors passively and allow tumor margins to be distinguished in a mouse model. In addition, it also exhibited an efficient laser-triggered photothermal therapy effect and . We thus propose that Mn-HDCL could have a role to play as a tumor-targeting photothermal sensitizer.
我们报告了一种稳定的、水溶性的单核锰(IV)配合物[Mn(H)]·5HO（Mn-HDCL），它是一种有效的光热材料。该体系基于一个六腙笼状配体（/HDCL），通过一种高效的一锅模板合成得到，避免了苛刻的反应条件的需要。扫描隧道显微镜图像显示，Mn-HDCL 存在于二维片状结构中。在 Mn-HDCL 中，锰(IV)离子被困在笼状配体的腔中。这有效地将 Mn(IV)离子屏蔽在外部环境之外，同时提供足够的水溶性。由于涉及配位锰(IV)离子的轨道跃迁以及金属-配体电荷转移效应，Mn-HDCL 具有大的消光系数，并表现出与固态单壁碳纳米管相当的光热性能。当在近红外 730nm 激光光照射下，在水溶液中实现了约 71%的高光热转换效率。Mn-HDCL 是顺磁性的，并在 和 中适度增加了磁共振图像的 T1 加权对比。在小鼠模型中发现，Mn-HDCL 能够被动靶向肿瘤，并能够区分肿瘤边缘。此外，它还表现出有效的激光触发光热治疗效果。因此，我们提出 Mn-HDCL 可以作为一种肿瘤靶向光热敏化剂发挥作用。
