Single crystal circular and linear dichroism spectra and absolute configuration of M(en)3(NO3)2(M = Zn(II), Cu(II), Ni(II), Co(II), Mn(II) and Ru(II)
The isomorphous single crystals of M(ethylenediamine)3(NO3)2, where M is Zn(II), Ni(II) and Co(II), exhibit macroscopic optical activity as predicted by their acentric space group. Axial circular dichroism measurements on these pure crystals show conclusively that spontaneous resolution has occurred. The axial circular dichroism and orthoaxial linear dichroism spectra of these pure crystals, and of Cu(II), Ni(II), Co(II), Mn(II) and Ru(II) doped into the Zn(en)3(NO3)2crystal have been measured at ambient and cryogenic temperatures in the range from 7 to 35 kK. The first NO3-transition at 32.5 kK is assigned as1A ←1A based on its linear polarization and sign of rotational strength. The d-d transitions are assigned in the context of D3symmetry and reveal a small negative crystal field parameter k, consistent with theoretical prediction. A positive R for all d-d transitions is found to be associated with the Λ configuration for all of the complex ions, by correlation with the crystal and solution circular dichroism of Ru(en)32+. © 1975.
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