论文标题
分子锚定在铜上稳定低价Ni（I）TPP在热诱导的化学变化上
Molecular anchoring stabilizes low valence Ni(I)TPP on copper against thermally induced chemical changes
论文作者
论文摘要
沉积在金属表面上的分子层的许多应用，范围从单原子催化到表面磁化学和生物传感，依赖于使用热周期来再生系统的原始特性。因此，了解有机/金属接口的热稳定性背后的微观起源对于工程可靠的有机设备是基础。在这里，我们研究铜表面上的镍卟啉分子作为一个原型系统，该系统包含一个金属中心，其氧化态可以通过与金属底物的相互作用来控制。我们证明，强的分子表面相互作用，然后在界面处进行电荷转移，通过将卟啉固定在底物上，在层的热稳定性中起着基本作用。热处理后，分子在420 K处进行不可逆的过渡，这与从底物的电荷转移增加有关，大多数位于苯基取代基上，而后者的下降却没有任何化学修饰。
Many applications of molecular layers deposited on metal surfaces, ranging from single-atom catalysis to on-surface magnetochemistry and biosensing, rely on the use of thermal cycles to regenerate the pristine properties of the system. Thus, understanding the microscopic origin behind the thermal stability of organic/metal interfaces is fundamental for engineering reliable organic-based devices. Here, we study nickel porphyrin molecules on a copper surface as an archetypal system containing a metal center whose oxidation state can be controlled through the interaction with the metal substrate. We demonstrate that the strong molecule-surface interaction, followed by charge transfer at the interface, plays a fundamental role in the thermal stability of the layer by rigidly anchoring the porphyrin to the substrate. Upon thermal treatment, the molecules undergo an irreversible transition at 420 K, which is associated with an increase of the charge transfer from the substrate, mostly localized on the phenyl substituents, and a downward tilting of the latters without any chemical modification
