Cationic Mn2+/H+ exchange leading a slow solid-state transformation of a 2D porphyrinic network at ambient conditions
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 transformat...
| Autores: | , , , , , , |
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| Tipo de recurso: | artículo |
| Fecha de publicación: | 2017 |
| País: | España |
| Institución: | Universidad del País Vasco |
| Repositorio: | Addi. Archivo Digital para la Docencia y la Investigación |
| OAI Identifier: | oai:addi.ehu.eus:10810/24025 |
| Acceso en línea: | http://hdl.handle.net/10810/24025 |
| Access Level: | acceso abierto |
| Palabra clave: | coordination polymer porphyrin structural analysis DFT calculations thermal analysis solvothermal synthesis |
| Sumario: | 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 sovent) 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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