Even-Numbered Metal Chain Complexes: Synthesis, Characterization, and DFT Analysis of [Ni4(μ4-Tsdpda)4(H2O)2] (Tsdpda2- = N-(p-toluenesulfonyl)dipyridyldiamido), [Ni4(μ4-Tsdpda)4]+, and Related Ni4 String Complexes

The synthesis and the X-ray structure of two complexes exhibiting a linear chain of four nickel atoms is reported, following Ni4(mu4-phdpda)4 (1), which had been characterized previously. [Ni4(mu4-Tsdpda)4(H2O)2], where H2Tsdpda is N-(p-toluenesulfonyl)dipyridyldiamine (2), is axially coordinated to two water molecules, at variance with 1. One-electron oxidation of 2 resulted in the loss of the axial ligands, yielding [Ni4(mu4-Tsdpda)4]+, [3]+, which was also structurally characterized. Finally, we report the structure of Ni4(mu4-DAniDANy)4 (4), a complex synthesized starting from the new ligand N,N'-bis-p-anisyl-2,7-diamino-1,8-naphthyridine. Magnetic measurements concluded that 4 is diamagnetic, like 1, whereas 2 is antiferromagnetic (-2J(14) = 80 cm(-)(1), using the Heisenberg Hamiltonian H = -2J(14) S(1).S(4)), as are other axially coordinated chains with an odd number of nickel atoms. DFT calculations are reported on these complexes in order to rationalize their electronic structure and their magnetic behavior. The magnetic properties of the [Ni4]8+ complexes are governed by the electronic state of the Ni(II) atoms, which may be either low-spin (S = 0), or high-spin (S = 1). DFT calculations show that the promotion to high spin of two Ni atoms in the chain, either external or internal, depends on the interplay between axial and equatorial coordination. The synergy between axial coordination and the presence of electron-withdrawing toluenesulfonyl substituents in 2 favors the promotion to the high-spin state of the terminal Ni atoms, thus yielding an antiferromagnetic ground state for the complex. This is at variance with complexes 1 and 4, for which the lowest quintet state results from the promotion to high spin of the internal nickel atoms, together with an important ligand participation, and is destabilized by 9 to 16 kcal mol(-1) with respect to the diamagnetic ground state.