Heterobimetallic {PtMn} and {PtFe} lantern complexes with exceptionally long metallophilic contacts.

• Heterobimetallic [PtM(SAc) 4 (L)] lantern complexes containing divalent Mn, Fe, Co, Ni, and Zn. • Exceptionally long Pt⋯Pt contacts for [PtM(SAc) 4 (pySMe)] with M = Fe, Co, Ni. • Antiferromagnetic coupling observed between [PtM(SAc) 4 (pySMe)] dimers. A new series of heterobimetallic lantern complexes, [PtM(SAc) 4 (pySMe)] (M = Mn (1), Fe (2), Co (3), Ni (4), Zn (5)), as well as additions to the previously reported series, [PtM(SAc) 4 (pyNH 2)] (M = Mn (6), Fe (7)), have been synthesized and thoroughly characterized. Notably, compounds 1 and 6 are the first crystallographically characterized, neutral Pt-Mn containing lantern complexes. Compounds 2 and 7 are the first examples of Pt-Fe containing lantern complexes with a pyridine based axial ligand. These newly synthesized complexes have been characterized by single-crystal X-ray diffraction and UV–vis (1 – 7), 1H and 13C NMR spectroscopies (5), and solution magnetic susceptibility (1 – 4 and 6 – 7) and analyzed in comparison to our previously reported lantern families. Compounds 2 – 4 are isomorphous and contain two crystallographically independent dimers with the same staggered conformations. One dimer has a typical Pt⋯Pt metallophilic interaction ranging from 3.2198(6) to 3.2913(6) Å while the other has a much longer contact ranging from 3.3212(6) to 3.4533(6) Å. These latter contacts suggest metallophilic interactions that are the longest reported to date in any system. Solid state variable-temperature magnetic susceptibility studies suggest antiferromagnetic coupling between the 3 d metal centers in the two lantern complexes of the dimeric forms of 2 , 3 , and 4. [ABSTRACT FROM AUTHOR]