We present a combined experimental and theoretical study of the nature of the proposed metal−metal bonding in the tetranuclear cluster Ni 4 (NP t Bu 3 ) 4 , which features four nickel(I) centers engaged in strong ferromagnetic coupling. High-resolution single-crystal synchrotron X-ray diffraction data collected at 25 K provide an accurate geometrical structure and a multipole model electron density description. Topological analysis of the electron density in the Ni 4 N 4 core using the quantum theory of atoms in molecules clearly identifies the bonding as an eight-membered ring of type [Ni−N−] 4 without direct Ni−Ni bonding, and this result is generally corroborated by an analysis of the energy density distribution. In contrast, the calculated bond delocalization index of ∼0.6 between neighboring Ni atoms is larger than what has been found for other bridged metal−metal bonds and implies direct Ni−Ni bonding. Similar support for the presence of direct Ni−Ni bonding is found in the interacting quantum atom approach, an energy decomposition scheme, which suggests the presence of stabilizing Ni−Ni bonding interactions with an exchange-correlation energy contribution approximately 50% of that of the Ni−N interactions. Altogether, while the direct interactions between neighboring Ni centers are too weak and sterically constrained to bear the signature of a topological bond critical point, other continuous measures clearly indicate significant Ni−Ni bonding. These metal−metal bonding interactions likely mediate direct ferromagnetic exchange, giving rise to the high-spin ground state of the molecule.

In recent years, Single Molecule Magnets (SMMs) have gained significant attention, primarily due to their potential technological applications in the field of information storage and processing. SMMs are molecules that behaves as small nanomagnets and represents the smallest possible bit that can be used to store binary information. A common method to increase the total spin of such molecule is by engaging several metal centers in a strong ferromagnetic coupling. This strategy is applied in a recent study [1] of the tetranuclear transition metal compounds with formulas M4(NP t Bu3)4 (M = Ni, Cu), and the oxidised forms, [M4(NP t Bu3)4] + . These results suggest a strongly coupled, large-spin ground state in the two nickel compounds.