Abstract
Electron paramagnetic resonance (EPR) and pulse electron–nuclear double resonance (ENDOR) spectroscopies are applied to investigate the structural phase transition and the low temperature phase in manganese- and copper-doped [NH3(CH2)4NH3][Zn(HCOO)3]2 dense metal–organic framework. Continuous-wave (CW) EPR measurements indicate successful incorporation of Mn2+ and Cu2+ ions at the Zn2+ lattice sites. Pulse ENDOR spectrum reveals at least four different proton species in the vicinity of the Mn2+ center showing excellent agreement with the X-ray diffraction experiments. Temperature-dependent CW EPR spectra demonstrate that Mn2+ and Cu2+ local paramagnetic probes are sensitive to the phase transition in the studied compounds. The analysis of the temperature dependence of the Cu2+ hyperfine coupling parameter reveals a first-order phase transition at Tc = 235 K into an antiferroelectric phase that is close to the tricritical point. The obtained logarithmic divergence of the line width of the Mn2+ EPR spectrum...
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