Understanding the influence of adsorption sites to the electronic properties of adsorbed molecules on two-dimensional (2D) ultrathin insulator is of essential importance for future organic-inorganic hybrid nanodevices. Here, the adsorption and electronic states of manganese phthalocyanine (MnPc) on a single layer of hexagonal boron nitride (h-BN) have been comprehensively studied by low-temperature scanning tunneling microscopy/spectroscopy and tight binding calculations. The frontier orbitals of the MnPc can change drastically by reversible manipulation of individual MnPc molecules onto and away from the single atomic vacancies at the h-BN surface. Particularly, the change of the molecular electronic configuration can be controlled depending on whether the atomic vacancy is below the metal center or the ligand of the MnPc. These findings give new insight into defect-engineering of the organic-inorganic hybrid nanodevices down to submolecular level.

理解吸附位点对二维（2D）超薄绝缘体上吸附分子的电子特性的影响，对于未来的有机-无机杂化纳米器件至关重要。在这里，已通过低温扫描隧道显微镜/光谱法和紧密结合计算对锰酞菁（MnPc）在六方氮化硼（h-BN）单层上的吸附和电子态进行了全面研究。MnPc的前沿轨道可以通过对单个MnPc分子进行可逆操作而使其在h-BN表面的单个原子空位上或远离该单个原子空位而发生急剧变化。特别地，可以根据原子空位是在金属中心还是在MnPc的配体以下来控制分子电子构型的变化。