In the pursuit of manipulating the properties of single atoms, the surface-supported metal–organic frameworks (MOFs) provide us opportunities to individually address the electronic and magnetic properties of coordinated metal atoms by scanning tunneling microscopy. Recently, we have synthesized Ni-TPyP (TPyP = 5,10,15,20-tetra-(4-pyridyl) porphyrin) networks with dinuclear Ni centers on a Au(111) surface, in which the top-Ni atoms are sitting above the molecular plane. Here, we investigate the top-Ni atoms and their hydrogenated derivatives by low-temperature scanning tunneling microscopy and spectroscopy, and show that the electronic and magnetic states of top-Ni atoms can be manipulated by hydrogen adsorption. Specifically, by fitting the spin-flip spectra in vertical magnetic field, we find the spin state of top-Ni atoms is tuned from S = 1/2 to S = 1 by attaching one H atom and S = 3/2 by attaching two H atoms. Our work demonstrates atomic-scale control over the electronic and magnetic properties of coordinated metal atoms in a surface-supported MOF.

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