Lanthanide-Dependent Photochemical and Photophysical Properties of Lanthanide–Anthracene Complexes: Experimental and Theoretical Approaches

The structural, photophysical, and photochemical properties of Ln(depma)(hmpa)₂(NO₃)₃ (Ln = La, Ce, Nd, Sm, Eu, Tb, Ho, Er, and Yb) complexes <b>1-Ln</b> were investigated with a multidisciplinary approach involving synthesis, photocycloaddition-based crystal engineering, spectroscopic analytical techniques and quantum chemical ab initio calculations. Depending on the Ln³⁺ ion the isostructural <b>1-Ln</b> complexes exhibit quite different behavior upon excitation at 350-400 nm. Some <b>1-Ln</b> complexes (Ln = La, Ce, Sm, Tb, Yb) emit a broad and strong band near 533 nm arising from paired anthracene moieties, whereas others (Ln = Nd, Eu, Ho, Er) do not. <b>1-Eu</b> is not emissive at all, whereas <b>1-Nd</b>, <b>1-Ho</b>, and <b>1-Er</b> exhibit a Ln³⁺ based luminescence. Upon irradiation with 365 nm ultraviolet (UV) light <b>1-Ln</b> (Ln = La, Ce, Sm, Tb, Yb) dimerize by means of a photochemically induced [4 + 4] cycloaddition of the anthracene moieties, whereas <b>1-Ln</b> (Ln = Nd, Eu, Ho, Er) remain monomers. We propose three models, based on the matching of the energy levels between the Ln³⁺ ion and the paired or dimerized anthracene units in the energy-resonance crossing region, as well as on internal conversion-driven and intersystem crossing-driven energy transfer, which explain the Ln³⁺ ion regulated photophysics and photochemistry of the <b>1-Ln</b> complexes.