Influence of Outer-Sphere Anions on the Photoluminescence from Samarium(II) Crown Complexes

Three samarium(II) crown ether complexes, [Sm(15-crown-5)₂]I₂ (1), [Sm(15-crown-5)₂]I₂·CH₃CN (2), and [Sm(benzo-15-crown-5)₂]I₂ (3), have been prepared via the reaction of SmI₂ with the corresponding crown ether in either THF or acetonitrile in good to moderate yields. The compounds have been characterized by single crystal X-ray diffraction and a variety of spectroscopic techniques. In all cases, the Sm(II) centers are sandwiched between two crown ether molecules and are bound by the five etheric oxygen atoms from each crown ether to yield 10-coordinate environments. Despite the higher symmetry crystal class of 1 (R3c), the samarium center resides on a general position, whereas in 2 and 3 (both in P2₁/c) the metal centers lie upon inversion centers. Moreover, the complexes in 2 and 3 are approximated well by D₅ symmetry. The molecule in 1, however, is distorted from idealized D₅ symmetry, and the crown ethers are more puckered than observed in 2 and 3. All three complexes luminesce in the NIR at low temperatures. However, the nature of the luminescence differs between the three compounds. 1 exhibits broadband photoluminescence at 20 °C but at low temperatures transitions to narrow peaks. 2 only exhibits nonradiative decay at 20 °C and at low temperatures retains a mixture of broadband and fine transitions. Finally, 3 displays broadband luminescence regardless of temperature. Spin-orbit (SO) CASSCF calculations reveal that the outer-sphere iodide anions influence whether broadband luminescence from 5d → 4f or fine 4f → 4f transitions occur through the alteration of symmetry around the metal centers and the nature of the excited states as a function of temperature.