CORTIJO, Miguel; VALENTÍN-PÉREZ, Ángela; ROUZIERES, Mathieu; CLÉRAC, Rodolphe; ROSA, Patrick; HILLARD, Elizabeth

doi:10.3390/cryst10060472

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CORTIJO, Miguel
Centre de Recherche Paul Pascal [CRPP]

VALENTÍN-PÉREZ, Ángela
Centre de Recherche Paul Pascal [CRPP]

ROUZIERES, Mathieu
Centre de Recherche Paul Pascal [CRPP]

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Crystals. 2020-06, vol. 10, n° 6, p. 472 (14 p.)

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Octahedral tris(ethylenediamine) coordination complexes demonstrate helicoidal chirality, due to the arrangement of the ligands around the metal core. The enantiomers of the nitrate salts [Ni(en)3](NO3)2 and [Zn(en)3](NO3)2 spontaneously resolve to form a mixture of conglomerate crystals, which present a reversible phase transition from space group P6322 to enantiomorphic P6522 or P6122, with the latter depending on the handedness of the enantiomer. We report here the synthesis and characterization of [Mn(en)3](NO3)2 and [Co(en)3](NO3)2, which are isostructural to the Zn(II) and Ni(II) derivatives. The Mn(II) analogue undergoes the same phase transition centered at 150(2) K, as determined by single-crystal X-ray diffraction, Raman spectroscopy, and differential scanning calorimetry. The Co(II) derivative does not demonstrate a phase transition down to 2 K, as evidenced by powder X-ray diffraction and heat capacity measurements. The phase transition does not impact the magnetic properties of the Ni(II) and Mn(II) analogues; these high spin compounds display Curie behavior that is consistent with S = 1 and 5/2, respectively, down to 20 K, while the temperature-dependent magnetic moment for the Co(II) compound reveals a significant orbital contribution.< Réduire

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phase transition

coordination complexes

enantiomorphic space groups

X-ray crystallography

chirality

conglomerate crystallization

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Tris(ethylenediamine) cobalt(II) and manganese(II) nitrates

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