Octahedral Coordinated Cluster TaN 12 + : Mass Spectrometry Detection, Photodissociation Observation, and Theoretical Exploration

The TaN n + cationic clusters were generated via laser ablation and analyzed using time‐of‐flight (TOF) mass spectrometry. The mass spectrometry experiment identified the TaN 12 + cluster as the dominant TaN compound, exhibiting the most intense peak. Photodissociation experiments on the TaN 12 + clusters with 266 nm (4.66 eV) photons revealed that the photodissociation fragment ion TaN 4 + was dominant in the spectrum. Density functional theory calculations revealed that TaN 12 + has an octahedral D 4h geometry symmetry with six N 2 ligands. The cluster features two distinct TaN bond lengths of 2.16 and 2.22 Å. Orbital analysis uncovers the origin of this asymmetry: the four coplanar N 2 ligands are strongly σ ‐bound and activated, whereas the two axial ones engage via weaker π‐interactions. Photodissociation pathway analysis established a reversible relationship between TaN 2 n + ( n = 1 − 6) clusters growth‐dissociation processes. Quantitative Hirshfeld charge and charge transfer analyses confirm Ta as a Lewis acid center with N 2 ligands functioning as Lewis bases. The spin‐density population indicates the presence of antiparallel coupling within the TaN 12 + cluster, leading to ferrimagnetism. Interaction region indicator analysis confirms the presence of well‐defined coordination bonds between the Ta atom and its ligands.