By means of a combined experimental and computational approach, we show that a 2D metal–organic framework self-assembled at the Au(111) termination is able to mimic the O₂ stabilization and activation mechanisms that are typical of the biochemical environment of proteins and enzymes. 5,10,15,20-tetra(4-pyridyl)21H,23H-porphyrin cobalt(III) chloride (CoTPyP) molecules on Au(111) bind dioxygen forming a covalent bond at the Co center, yielding charge injection into the ligand by exploiting the surface trans-effect. A weakening of the O–O bond occurs, together with the development of a dipole moment, and a change in the molecule’s magnetic moment. Also the bonding geometry is similar to the biological counterpart, with the O₂ molecule sitting on-top of the Co atom and the molecular axis tilted by 118°. The ligand configuration lays between the oxo- and the superoxo-species, in agreement with the observed O–O stretching frequency measured in situ at near-ambient pressure conditions.

通过组合的实验和计算方法，我们显示了在Au（111）末端自组装的2D金属-有机骨架能够模仿O ₂稳定和激活机制，这是蛋白质和蛋白质生化环境的典型特征。酶。Au（111）上的5,10,15,20-四（4-吡啶基）21H，23H-卟啉氯化钴（III）分子结合双氧在Co中心形成共价键，从而将电荷注入配体通过利用表面反作用。O-O键的减弱会发生，偶极矩也会形成，分子的磁矩也会发生变化。另外，键的几何形状类似于生物学的对应物，其中O ₂分子位于Co原子的顶部，分子轴倾斜118°。配体构型位于含氧和超含氧物种之间，这与在接近环境压力条件下原位测得的O–O拉伸频率一致。