We report the synthesis, crystal structure, and thermal, dielectric, phonon, and magnetic properties of [NH2-CH(+)-NH2][Mn(HCOO)3] (FMDMn). The anionic framework of [(Mn(HCOO)3(-)] is counterbalanced by formamidinium (FMD(+)) cations located in the cavities of the framework. These cations form extensive N-H···O hydrogen bonding with the framework. The divalent manganese ions have octahedral geometry and are bridged by the formate in an anti-anti mode of coordination. We have found that FMDMn undergoes a structural phase transition around 335 K. According to the X-ray diffraction, the compound shows R3̅c symmetry at 355 K and C2/c symmetry at 295 and 110 K. The FMD(+) cations are dynamically disordered in the high-temperature phase, and the disorder leads to very large bandwidths of Raman and IR bands corresponding to vibrations of the NH2 groups. Temperature-dependent studies show that the phase transition in FMDMn is associated with ordering of the FMD(+) cations. Detailed analysis shows, however, that these cations still exhibit some reorientational motions down to about 200 K. The ordering of the FMD(+) cations is associated with significant distortion of the anionic framework. On the basis of the magnetic data, FMDMn is a weak ferromagnet with the critical temperature Tc = 8.0 K.

Novel heterometallic formate [(CH3)2NH2][Fe(III)Mg(II)(HCOO)6] (DMFeMg) was prepared and characterized by single crystal X-ray diffraction, DSC, dielectric, magnetic susceptibility, Raman and IR methods. We also report thermal, Raman and IR studies of the known compound [(CH3)2NH2][Fe(III)Fe(II)(HCOO)6] (DMFeFe). DMFeMg crystallizes in the niccolite structure (P3[combining macron]1c space group). In contrast to the known DMFeFe, [(CH3)2NH2][Fe(III)Mn(II)(HCOO)6] (DMFeMn) and [(CH3)2NH2][Fe(III)Co(II)(HCOO)6] (DMFeCo) formates, the metal ions in DMFeMg are distributed statistically over the two available octahedral sites. Temperature-dependent studies show that whereas DMFeFe exhibits an order-disorder phase transition at 151.8 K upon cooling, freezing-in of re-orientational motions of DMA(+) cations does not lead to any structural phase transition in DMFeMg. We discuss the origin of this difference. The low-temperature studies also show that DMFeMg orders magnetically at TC = 13.5(5) K and the shape of M(T) measured in the field-cooling regime suggests ferromagnetic character of the ordering.

Mixed-valence iron(ii)–iron(iii) formate framework templated by diethylammonium cations exhibit structural and magnetic phase transitions near 240 and 39 K, respectively.

We report the synthesis, crystal structure, and dielectric, vibrational and emission spectra of two novel heterometallic perovskite-type metal-organic frameworks (MOFs) of the following formula: [(CH)NH][KCr(HCOO)] (DMAKCr) and [CHNH][KCr(HCOO)] (EtAKCr). DMAKCr crystallizes in a trigonal structure (R3[combining macron] space group) and undergoes an order-disorder phase transition to the monoclinic system (P1[combining macron] space group) at about 190 K. The dielectric studies confirm the presence of first-order relaxor-like structural transformation. In the high-temperature phase, the dimethylammonium cations are dynamically disordered over three equal positions and upon cooling the dynamical disorder evolves into a two-fold one. This partial ordering is accompanied by a small distortion of the metal-formate framework. EtAKCr crystallizes in a monoclinic structure (P2/n space group) with ordered EtA cations and does not experience any phase transition. The differences in the thermal behavior caused by the substitution of Na ions by larger K ions in the [cat]MM (cat = DMA, EtA, M = Na, K and M = Cr and Fe) heterometallic MOF family are discussed taking into account the impact of the hydrogen bond (HB) pattern and other factors affecting the stability of metal-formate frameworks. The optical studies show that DMANaCr and EtAKCr exhibit Cr-based emission characteristics for intermediate ligand field strength.