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Investigation of structure-properties relationship in a novel family of halogenoantimonates(III) and halogenobismuthates(III) with morpholinium cation: [NH2(C2H4)2O]MX4. Crystal structure, phase transitions and dynamics of molecules.

Autorzy

Magdalena T. Owczarek

Ryszard Jakubas

Adam Pietraszko

Wojciech Medycki

Jan Baran

Rok wydania

2013

Czasopismo

Dalton Transactions

Numer woluminu

42

Strony

15069-15079

DOI

10.1039/c3dt51726h

Kolekcja

Naukowa

Język

Angielski

Typ publikacji

Artykuł

Streszczenie

Three new organic-inorganic hybrids based on halogenoantimonates(III) and halogenobismuthates(III) with the morpholinium cation, [NH2(C2H4)2O]SbCl4, [NH2(C2H4)2O]SbBr4 and [NH2(C2H4)2O]BiBr4, have been prepared and characterized with DSC, TGA, DTA and single-crystal X-ray diffraction. The common feature of the crystal structures of the studied compounds is the presence of polyanionic ([MX4]∞(-)) and morpholinium (head-to-tail configuration) chains, which expand themselves parallel to each other. The antimonate derivatives are isomorphous, crystallizing in a centrosymmetric orthorhombic Pbca space group and show no phase transitions (PTs) between 110 and 370 K. On the other hand, [NH2(C2H4)2O]BiBr4 undergoes two first-order structural PTs: I ↔ II at 321/343 K (cooling/heating) and II ↔ III at 285/289 K (cooling/heating). The mechanism of the PTs is discussed on the basis of crystallographic data and (1)H NMR and infrared spectroscopy. The PT at 343 K is accompanied by a spectacular switching of the spin-lattice T1 relaxation pathway. Structural parameters analysis has been performed to discuss a structure-properties relationship.

Adres publiczny

http://dx.doi.org/10.1039/c3dt51726h

Strona internetowa wydawcy

https://www.rsc.org/

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