Encapsulation of Porphyrin-Fe/Cu Complexes into Coordination Space for Enhanced Selective Oxidative Dehydrogenation of Aromatic Hydrazides.

The encapsulation of specific nanoentities into hollow nanomaterials derived from metal organic frameworks has attracted continuous and growing research attentions owing to their unique structural properties and unusual synergistic functions. Herein, using the phase transformation of uniform rhombi dodecahedron ZIF-67, hollow nano-shell with a well-defined morphology is successfully prepared. Particularly, the iron-oxygen complex, that is formed by the interaction between TCPP-Fe/Cu (TCPP = tetrakis(4-carboxyphenyl)-porphyrin) and oxygen, can be acted as an ideal proton acceptor for practical organic reactions. Considering the unique adaptability of hollow ZIFs (named HZ) to the transformation of encapsulated TCPP-Fe/Cu bimetallic catalytic active sites, a heterogeneous catalyst (defined as HZ@TCPP-Fe/Cu) through morphology-controlled thermal transformation and rear assemble processes is designed and constructed. Under heterogeneous conditions, HZ@TCPP-Fe/Cu serves as a multifunctional molecular selector to promote the oxidative dehydrogenation of different aromatic hydrazide derivatives with high selectivity toward primary carbon among primary, secondary, and tertiary carbons that are unachievable by other traditional homogeneous catalysts. The high catalytic activity, selectivity, and recyclability of the catalyst proposed here are attractive advantages for an alternative route to the environmentally benign transformation of aromatic hydrazides to aromatic azobenzene.