Photophysical and Magnetic Properties in Zero-Dimensional (H2DABCO)MX4•nH2O (M = Mn and Cu; X = Cl and Br; n=0, 1, and 4)

We report five new manganese and copper organic-inorganic hybrid (OIH) halides based on 1,4-diazabicyclo[2.2.2]octane (DABCO: C6H12N2). The materials obtained have general formula (H(2)DABCO)MX4 center dot nH(2)O where M = Mn and Cu, X = Cl and Br, and n = 0, 1, and 4. The compounds (H(2)DABCO)MnX4 center dot 4H(2)O (X = Cl and Br) crystallize in a chiral P2(1)2(1)2(1) structure with unique zero-dimensional (0D) manganese octahedra, whereas anhydrous (H(2)DABCO)MnBr4 exhibits a monoclinic crystal structure (space group P2(1)/c) with isolated MnBr4 tetrahedra. While (H(2)DABCO)MnCl4 center dot 4H(2)O is nonluminescent, the bromine analogue displays red emission with a photoluminescence quantum yield (PLQY) of 10.8%. Interestingly, anhydrous (H(2)DABCO)MnBr4 demonstrates intense green emission due to the tetrahedral coordination of Mn2+ ion. The PLQY for (H(2)DABCO)MnBr4 is 52.16%, and it shows a longer lifetime of the photoexcited electrons than the hydrated compound. In contrast, the copper OIH halides (X = Cl and Br) reveal an identical 0D tetrahedral structure crystallizing with one water molecule in the P2(1)/c space group. Both manganese and copper OIH halides exhibit a magnetocaloric effect at low temperatures.