Realization of Unusual Ligand Binding Motifs in Metalated Container Molecules: Synthesis, Structures, and Magnetic Properties of the Complexes [(LMe)Ni₂(μ‐L′)]n+ with L′=NO₃⁻, NO₂⁻, N₃⁻, N₂H₄, Pyridazine, Phthalazine, Pyrazolate, and Benzoate

A series of dinickel(II) complexes with the 24-membered macrocyclic hexaazadithiophenol ligand H(2)L(Me) was prepared and examined. The doubly deprotonated form (L(Me))(2-) forms complexes of the type [(L(Me))Ni2II(mu-L')](n+) with a bioctahedral N(3)Ni(II)(mu-SR)(2)(mu-L')Ni(II)N(3) core and an overall calixarene-like structure. The bridging coordination site L' is accessible for a wide range of exogenous coligands. In this study L'=NO(3)(-), NO(2)(-), N(3)(-), N(2)H(4), pyrazolate (pz), pyridazine (pydz), phthalazine (phtz), and benzoate (OBz). Crystallographic studies reveal that each substrate binds in a distinct fashion to the [(L(Me))Ni(2)](2+) portion: NO(2)(-), N(2)H(4), pz, pydz, and phtz form mu(1,2)-bridges, whereas NO(3)(-), N(3)(-), and OBz(-) are mu(1,3)-bridging. These distinctive binding motifs and the fact that some of the coligands adopt unusual conformations is discussed in terms of complementary host-guest interactions and the size and form of the binding pocket of the [(L(Me))Ni(2)](2+) fragment. UV/Vis and electrochemical studies reveal that the solid-state structures are retained in the solution state. The relative stabilities of the complexes indicate that the [(L(Me))Ni(2)](2+) fragment binds anionic coligands preferentially over neutral ones and strong-field ligands over weak-field ligands. Secondary van der Waals interactions also contribute to the stability of the complexes. Intramolecular ferromagnetic exchange interactions are present in the nitrito-, pyridazine-, and the benzoato-bridged complexes where J=+6.7, +3.5, and +5.8 cm(-1) (H=-2 JS(1)S(2), S(1)=S(2)=1) as indicated by magnetic susceptibility data taken from 300 to 2 K. In contrast, the azido bridge in [(L(Me))Ni(2)(mu(1,3)-N(3))](+) results in an antiferromagnetic exchange interaction J=-46.7 cm(-1). An explanation for this difference is qualitatively discussed in terms of bonding differences.