Journal
CHIRALITY
Volume 24, Issue 12, Pages 1055-1062Publisher
WILEY-BLACKWELL
DOI: 10.1002/chir.22097
Keywords
ultaviolet CD; exciton CD; solvent effect; alkali metal ions dependence; concentration dependence; absolute configuration; diastereoselective formation
Funding
- National Institute of Health, Minority Biomedical Research Support [1SC3 GM089589-03, 3S06 GM008192-27S1]
- Henry Dreyfus Teacher-Scholar Award
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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 p-p* transition of MLn were examined in view of the solvent effect. Here, the concentration, alkali metal, and ammonium ion dependences are compared with the solid CD, 5D0???7F0(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 CH3CN solutions or between the SAPR-8-M-Ln and DD-D2d(mmmm)-8-M-Ln complexes in CHCl3 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. Chirality 24:10551062, 2012. (c) 2012 Wiley Periodicals, Inc.
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