ABSTRACT
Six lanthanide complexes constructed from two chiral ß-diketonates (d/l-fbc = 3-heptafluorobutyryl-(+)/(-)-camphorate), the stilbene derivative (E)-N',N'-bis(pyridin-2-ylmethyl)-4-styrylbenzoyl hydrazide (L), a trifluoroacetate anion (CF3CO2 -), and one water molecule, namely [Ln(d/l-fbc)2(L)(CF3CO2)]·H2O (LnC57H54F17N4O8, Ln = La (1, d-fbc), La (2, l-fbc), Sm (3, d-fbc), Eu (4, d-fbc), Eu (5, l-fbc), and Tb (6, d-fbc), were synthesized and characterized by single-crystal X-ray diffraction, 1H-NMR, elemental analysis, IR and UV-vis spectroscopy, and thermal gravimetric analysis. The photoisomerization reactions of these complexes were systematically studied by means of experimental and theoretical calculations. Crystals of complexes 1, 2, 3, and 4 were obtained and belong to the monoclinic crystal system and the C2 chiral space group. The Λ- and Δ-diastereomers coexist in their crystals and no apparent bisignate couplets are observed in their ECD spectra. Among the complexes, the photocyclization reaction is followed by the trans-to-cis photoisomerization reaction and competes with the trans-to-cis photoisomerization, then the photocyclization reaction continues. The photocyclization reaction is irreversible in this stilbene derivative and is delayed in the lanthanide complexes. These results provide a viable strategy for the design of promising new stilbene-attached dual-functional lanthanide-based optical-switching materials.
ABSTRACT
Five lanthanide complexes constructed from a stilbene derivative, (E)-N',N'-bis(pyridin-2-ylmethyl)-4-styrylbenzoyl hydrazide (HL), and two ß-diketonates (2-thenoyltrifluoroacetonate, tta), with or without a trifluoroacetate anion (CF3CO2 -), namely, [Ln(tta)2(HL) (CF3CO2)] [LnC45H32F9N4O7S2, Ln = La (1), Nd (2), Eu (3), or Gd (4)] and [Yb(tta)2(L)] (YbC43H31F6N4O5S2 (5), L = deprotonated HL), were synthesized and characterized. Crystals of these five complexes were obtained and analyzed by single-crystal X-ray diffraction. These complexes all belonged to the monoclinic P21/c space group. For La3+, Nd3+, Eu3+, and Gd3+, the central lanthanide ion was nine-coordinate with a monocapped twisted square antiprism polyhedron geometry. The central Yb3+ ion of complex 5 was eight-coordinate with a distorted double-capped triangular prism polyhedron geometry. Among the five complexes, trans-to-cis photoisomerization of the stilbene group in gadolinium complex 4 showed the largest quantum yield. Complexes 2, 3, and 4 showed dual luminescence and photoisomerization functions. The luminescence change of complex 3 was reversible upon the trans-to-cis photoisomerization process. The sensitization efficiencies of luminescent europium complex 3 in acetonitrile solutions and in the solid state were 49.9 and 42.6%, respectively. These medium sensitization efficiencies led to the observation of simultaneous photoisomerization and luminescence, which further confirmed our previous report that photoisomerization of the stilbene group within complexes was related to the lanthanide ion energy level and whether a ligand-to-metal center or ligand-to-ligand charge-transfer process was present. In complexes 1-5, in addition to the intramolecular absorption transition of the ligand itself (IL, πHL-πHL * and πtta-πtta*), the presence of a ligand-to-ligand charge-transfer transition between tta and HL (LLCT, πtta-πHL * or πHL-πtta *) indicated whether the triplet-state energy of HL was able to transfer to the excited energy level of the lanthanide ions, leading to different extents of HL photoisomerization. These results provide an important route for the design of new dual-function lanthanide-based optical switching materials.
