Magnetic Coupling between Metal Spins through the 7,7,8,8‐Tetracyanoquinodimethane (TCNQ) Dianion

A family of magnetic metal-organic frameworks, (Ph3PMe)2[M2(TCNQ)3] {M=Fe(2+), Co(2+), Ni(2+) and Zn(2+)} have been prepared and structurally characterized. The honeycomb-like "layers" consist of M(II) ions doubly bridged with dinitrilomethane moieties of two 7,7,8,8-tetracyanoquinodimethane (TCNQ) dianions which are further connected through phenyl rings to form a 3D dianionic framework [M2TCNQ3](2-) with Ph3PMe(+) cations filling cavities that run along the c axis. Studies of the magnetic coupling through the TCNQ dianion in these structures revealed that it can promote long-range magnetic ordering despite the long coupling pathway.