Zero-valent metals in metal–organic frameworks: fac-M(CO)3(pyrazine)3/2.

We report the synthesis of pyrazine-pillared metal–organic frameworks (MOFs) generated through ligand substitution of the Group 6 metal hexacarbonyls. The obtained frameworks exhibit hexagonal pore channels with CO-plastered porewalls. This series constitutes the first crystallographically characterized examples of Cr(0), Mo(0), and W(0)-based MOFs and suggests the exploration of homoleptic metal carbonyls as starting materials to generate polymeric materials with low-valent metal nodes. [ABSTRACT FROM AUTHOR]