A novel type of transition bimetal–organic frameworks was described as a heterogeneous catalyst for the oxidative coupling of amines to imines under mild conditions, which was easily synthesized by the coordination assembly of manganese(II) and cobalt(II) with 1,3,5-benzenetricarboxylic acid (H3BTC) for the first time. The metal–organic framework material was characterized by scanning electron microscopy, energy dispersive spectroscopy, X-ray photoelectron spectroscopy, X-ray diffraction, thermogravimetry and N2 sorption. As an environmentally benign heterogeneous catalyst, the catalytic ability of the metal–organic framework material was then detected to be excellent for the tert-butyl hydroperoxide (TBHP) promoted direct oxidative coupling of benzylamines to imines in excellent yields (up to 100%) in methanol for 3 h. More importantly, it could be recycled up to six runs, while still maintaining its high catalytic activity.
