Chiroptical Spectra of Tetrakis (+)-3-Heptafluorobutylrylcamphorate Ln(III) Complexes with an Encapsulated Alkali Metal Ion: Solution Structures as Revealed by Chiroptical Spectra

The preparation of tetrakis((+)-hfbc) lanthanide(III) complexes with an encapsulated alkali metal and ammonium ions M[Ln((+)-hfbc)(4)] (hereafter abbreviated as M-Ln : (+)-hfbc, (+)-heptafluorobutyrylcamphorate; M, ammonium or benzyl ammonium ions as well as alkali metal ions) was reported and discussed. The electronic circular dichroism (CD) spectra in the intraligand π-π* transition of M-Ln were examined in view of the solvent effect. Here, the concentration, alkali metal, and ammonium ion dependences are compared with the solid CD, (5)D(0)←(7)F(0) (Eu(III)) excitation spectra, circularly polarized luminescence, and vibrational circular dichroism. It has been revealed that the dodecahedral eight coordinate DD-8-M-Ln complexes in crystals are equilibrated between the diastereoselectively formed square antiprism eight coordinate SAPR-8-M-Ln and [Ln((+)-hfbc)(3)] in EtOH and CH(3) CN solutions or between the SAPR-8-M-Ln and DD-D(2d) (mmmm)-8-M-Ln complexes in CHCl(3) solution. The observed CD couplets are found to reflect the exciton CD couplets which are useful to determine the four-bladed SAPR-(llll) absolute configuration around the lanthanide(III) ion.