Issue 5, 2015

Towards multicomponent MOFs via solvent-free synthesis under conventional oven and microwave assisted heating

Abstract

Herein we prove the efficiency of the oven heating solvent-free synthesis, based on the acid–base reaction between a metal oxide/hydroxide, adenine (HAde) and monocarboxylic acids, to afford otherwise not accessible new MBioFs of formula [M23-Ade)22-OOC(CH2)xCH3)2]n expressed as 1_M@monocarboxylate [M(II): Ni or Zn; monocarboxylate: butanoato (But) and propanoato (Prop)]. Additionally, a microwave assisted solvent-free procedure has been carried out, leading to products with a somewhat lower adsorption performance but with the advantages of reducing the reaction times to the minute scale and incorporating randomly distributed additional meso/macropores generated during the release of the water vapour by-product. Both heating techniques provide the resulting products in a monolithic form. The N2 (77 K) and CO2 (273 K) adsorption isotherms indicate a great selectivity towards CO2 for the 1_Ni@But compound. On the other hand, a careful control over the solvent-free conditions provided good-quality single crystals of three new compounds based on the metal/nucleobase/carboxylate system: [Zn33-Ade)2(μ-OOCCH3)4]n·3H2O (2), [Zn(μ-Hypo)(μ-OOCCH3)]n (3) (Hypo: hypoxanthinate) and [Ni2(μ-HAde)2(μ-OOCH)2(OOCH)2(OH2)2]·2{(H2Ade)(HCOO)}·2HCOOH (4). Compounds 2 and 3 show lamellar structures without accessible voids. Compound 4 represents an intermediate stage between the initial reagent mixture and the final extended coordination polymers that depicts an insight into the reaction mechanism of the solvent-free approach. It also shows the difficulties in stabilizing the porous structure of 1 when short aliphatic monocarboxylic acids, such as acetic and formic acids, are employed.

Graphical abstract: Towards multicomponent MOFs via solvent-free synthesis under conventional oven and microwave assisted heating

Supplementary files

Article information

Article type
Chemistry Frontiers
Submitted
21 nov. 2014
Accepted
08 feb. 2015
First published
11 feb. 2015

Inorg. Chem. Front., 2015,2, 425-433

Author version available

Towards multicomponent MOFs via solvent-free synthesis under conventional oven and microwave assisted heating

M. Lanchas, S. Arcediano, G. Beobide, O. Castillo, A. Luque and S. Pérez-Yáñez, Inorg. Chem. Front., 2015, 2, 425 DOI: 10.1039/C4QI00208C

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