An EPR investigation of the phase transitions and cooperative ordering phenomena of pentaamminecopper(II) polyhedra in Cu(NH3)5X2 [X=BF4, CIO4; Br]

The results of powder and single-crystal EPR studies on Cu(NH3)5X2 compounds [X=BF4, CIO4; Br] give evidence that phase transitions from a cubic α-phase (g i ≃2.12) with an anti-K2PtCl6 type structure to low-temperature β-phases with reduced symmetry occur, which are induced by ordering processes of the vacancies □ of elongated [Cu(NH3)5□]2+ pseudo-octahedra. The type of order is crucially controlled, by the nature of the anion. In the case of the BF 4 − and ClO 4 − salts the large anions are structure-determining leading to a slightly disturbed antiferrodistortive order of the elongated CuIIN5 square pyramids atT c≃155 K and <130 K, respectively. The resulting pseudo-tetragonal β-structure…