Synthesis and Fluorescence Studies of Diborene Coinage Metal Complexes

Nine different coinage metal (Cu, Ag) π complexes of diborenes with various anionic diborene (aryl, heteroaryl) and metal substituents (Cl, Br, C₆F₅, C₂SiMe₃), stabilizing neutral donors (N-heterocyclic carbene = NHC, phosphine), configurations (cis/trans, acyclic/cyclic diborene), and charges (neutral, cationic) were synthesized and characterized by multinuclear NMR spectroscopy and X-ray crystallographic analyses. Their optical properties were investigated by UV-vis absorption and steady-state as well as time-resolved luminescence spectroscopy in solution and the solid state to gain insights into the excited-state behavior of this unusual class of photoactive compounds and to provide structure-property relationships. The structural and electronic modification of the (B═B)···M motif greatly influences not only the visible light absorption but also the photostability and quantum yields, which can reach high values of up to f = 0.42. The lifetimes are found in the nanosecond regime, providing estimated radiative rate constants over a wide range of k_r = 1.3-14 × 10⁷ s^-1, indicative of fluorescence. Intersystem crossing (ISC) is sufficiently slow for prompt emission from the S₁ state to be observed, while the spin-orbit coupling in the T₁ state is too weak for phosphorescence to occur at room temperature. ISC can be accelerated, however, by modifying diborene ligand substitution and the coinage metal center, hinting at the potential for exploiting the properties of long-lived triplet excited states of metal diborene complexes in the future.