Incorporation of Pyrazine and Bipyridine Linkers with High-Spin Fe(II) and Co(II) in a Metal–Organic Framework

A series of isoreticular metal–organic frameworks (MOFs) of the formula M­(BDC)­(L) (M = Fe­(II) or Co­(II), BDC = 1,4-benzenedicarboxylate, L = pyrazine (pyz) or 4,4′-bipyridine (bipy)) has been synthesized and characterized by N2 gas uptake measurements, single crystal and powder X-ray diffraction, magnetometry, X-ray absorption spectroscopy, and Mössbauer spectroscopy. These studies indicate the formation of a permanently porous solid with high-spin Fe­(II) and Co­(II) centers that are weakly coupled, consistent with first-principles density functional theory calculations. This family of materials represents unusual examples of paramagnetic metal centers coordinated by linkers capable of mediating magnetic or electronic coupling in a porous framework. While only weak interactions are observed, the rigid 3D framework of the MOF dramatically impacts the properties of these materials when compared with close structural analogues.