Cationic Mn2+/H+ exchange leading a slow solid-state transformation of a 2D porphyrinic network at ambient conditions

by / Wednesday, 12 July 2017 / Published in

Cationic Mn2+/H+ exchange leading a slow solid-state transformation of a 2D porphyrinic network at ambient conditions


Published in: Journal of Solid State Chemistry, 247, 161-167
2017/03/01
Publisher URL: http://www.sciencedirect.com/science/article/pii/S0022459617300142
DOI: https://doi.org/10.1016/j.jssc.2017.01.012 Authors:
Eder Amayuelas Arkaitz Fidalgo-Marijuan Begoña Bazán Miren-Karmele Urtiaga Gotzone Barandika Luis Lezama María Isabel Arriortua
Abstract:

Metalloporphyrins exhibit outstanding chemical, physical and biological properties in dissolution, however, it is a challenge to synthesize them as stable solid frameworks. Long-time stability is crucial for future applications of these materials, and we have detected a slow, solid-state transformation of a 2D MnII-porphyrin at RT. The remarkable point is that this transformation showed up as a result of Electronic Paramagnetic Resonance measurements. Otherwise, the evolution of the system could have remained undetected. Thus, 2D [Mn3(TCPP)(H2O)4]·nD (1) (where TCPP is meso-tetra(4-carboxyphenyl)porphyrin and D is the solvent) has been synthesized hydrothermally, and characterised by means of X-ray diffraction (XRD), Thermogravimetry and X-ray thermodiffractometry (XRTD). This compound slowly transforms into [Mn(H4TCPP)(H2O)2]·nD (2) according to the equilibrium [Mn3(TCPP)]+4H+[Mn(H4TCPP)]+2Mn2+. The evolution of the system has been studied through analysis of the distortion (both of the coordination sphere and the tetrapyrrolic macrocycle) and Density Functional Theory (DFT) quantum mechanical calculations.

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