μ2‐η1:η1‐N2 Bridged Bimetallic Dinitrogen Complexes: Geometry of the First Excited State in Connection to N2 π‐Photoactivation

Bimetallic end-on μ₂ -η¹ :η¹ -N₂ bridging dinitrogen complexes have served as the platform for photochemical N₂ activation, mainly for the N-N cleavage. However, the alternate N-N π-photoactivation route has remained largely unexplored. This study strengthens the notion of weakening the N-N bond through the population of π* orbital upon electronic excitation from the ground to the first excited state using four prototypical complexes based on Fe (1), Mo (2), and Ru (3,4). The complexes 1-4 possess characteristic N-N π* based LUMO (π*-π*-π*) centered on their M-N-N-M core, which was earlier postulated to play a central role in the N₂ photoactivation. Vertical electronic excitation of the highest oscillator strength involves transitions to the N-N π*-based acceptor orbital (π*-π*-π*) in complexes 1-4. This induces geometry relaxation of the first excited metal-to-nitrogen (π*) charge transfer (¹ MNCT) state leading to a "zigzag" M-N-N-M core in the equilibrium structure. Obtaining the equilibrium geometry in the first excited state with the full-sized complexes widens the scope of N-N π-photoactivation with μ₂ -η¹ :η¹ -N₂ bridging dinitrogen complexes. Promisingly, the elongated N-N bond and bent ∠MNN angle in the photoexcited S₁ state of 1-4 resemble their radical- and di-anion forms, which lead toward thermodynamically feasible N-N protonation in the S₁ excited state.