Matrix Isolation Chemistry in a Porous Metal−Organic Framework:  Photochemical Substitutions of N2 and H2 in Zn4O(η6-1,4-Benzenedicarboxylate)Cr(CO)33

Reaction of the microporous metal-organic framework Zn4O(BDC)3 (BDC2- = 1,4-benzenedicarboxylate) with Cr(CO)6 at 140 degrees C in a 6:1 mixture of dibutylether and THF affords Zn4O(BDC)Cr(CO)33 (1). This compound retains the porous cubic structure of the parent framework, but features Cr(CO)3 groups attached in an eta6 fashion to all of the benzene rings. Compound 1 is also microporous, exhibiting a BET surface area of 2130 m2/g. It can be fully decarbonylated by heating at 200 degrees C, but the resulting gray solid (2) shows little affinity for N2 or H2 at 298 K, suggesting aggregation of the chromium atoms. In contrast, photolysis of 1 using 450-nm light in an atmosphere of N2 or H2 produces solids with infrared spectra indicative of Zn4O(BDC)Cr(CO)2(N2)3 (3) and Zn4O(BDC)Cr(CO)2(H2)3 (4). Under an N2 atmosphere, compound 4 completely converts into compound 3 over the course of 12 h, demonstrating the lability of the Cr0-H2 bond. Owing to isolation of the metal centers within the rigid, evacuable framework structures, the N2- and H2-substituted compounds show greatly enhanced stability relative to molecular analogues generated in frozen gas matrices or supercritical fluid solutions.