Rh3+-doped NaCl single crystals grown from aqueous solution were studied with electron paramagnetic resonance and electron nuclear double resonance after irradiation at liquid nitrogen temperature. [RhCl6]4− complexes with two next-nearest neighbor charge compensating vacancies have been detected. The two vacancy-Rh2+ axes make an angle of 900 to each other and are perpendicular to the center symmetry axis. After warming the sample, this center with C2v symmetry decays consecutively into two other [RhCl6]4− centers reported earlier in Rh3+-doped NaCl and AgCl Bridgman crystals on the one hand, and/or in solution-grown NaCl:Rh3+ crystals irradiated at room temperature on the other hand.

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