Some basic correlations in the thermal (kinetic) stability of inclusion compounds on the basis of microporous metal–organic frameworks Vladimir Logvinenko 1,2 • Marina Zavakhina 1 • Vsevolod Bolotov 1 • Denis Pishchur 1 • Danil Dybtsev 1,2 Received: 21 December 2016 / Accepted: 17 March 2017 Ó Akade ´miai Kiado ´, Budapest, Hungary 2017 Abstract Metal–organic frameworks (MOFs) have promising practical applications in gas storage, separation and purification, and catalysis. The standard process for MOF production begins with the synthesis of the inclusion compound. The molecules of the organic solvent used are caught in the channels and caves of the MOF structure. These primary inclusion guest molecules are excluded further by the evacuation or by the heating. We investigate a series of inclusion compounds and study the correlation between their thermal (kinetic) stability and the framework and guest molecule properties. Thermogravimetric curves are used for the kinetic studies. Kinetic parameters of decomposition are estimated within the approaches of non- isothermal kinetics (‘‘model-free’’ kinetics and nonlinear regression methods). We discuss guest molecular kinetic diameters, guest molecule sizes, shape and polarity, the guest phase state (fluid or solid) within the framework pores, the flexibility of the framework structures, the enthalpy and entropy contributions to the kinetic stability and the inclusion compound properties with very similar frameworks (channel walls with similar chemical consti- tutions), but with different channels length. Keywords Inclusion compounds  Molecular kinetic diameters  Kinetic stability  Metal–organic frameworks  Non-isothermal kinetics Introduction Metal–organic coordination polymers (MOFs) are com- pounds with infinite structures built from organic and inorganic units. Porous metal–organic frameworks are now of significant interest because of the wide opportunities of combining metals and ligands in their synthesis that allow for the production of coordination polymers with extended surface areas and the tuning of the size and shape of the pores [1, 2]. Depending on the structure, such materials can serve as matrices for the inclusion of specific guest mole- cules, which highlights their unique properties and various potential applications. Porous coordination polymers are widely studied as materials for gas storage [3–6], separa- tion [7, 8], catalysts [9, 10] and sensors [11, 12]. The ability of metal–organic frameworks to include ions and mole- cules of different sizes leads to their application in ion exchange [13], drug delivery [14, 15], proton conductivity [16] and other areas. All these potential applications are determined not only by the attributes of the framework itself, but also by the interaction of the coordination polymer and guests. The presence of the guest molecules can have a significant influence on the coordination poly- mer structure [17] and greatly contribute to the properties of the resulting inclusion compound [18]. Thus, for the investigation of the properties of a host–guest system, the polymer framework and the guest composition should be studied in complex. Versatile research on this topic is important for understanding the principles of host–guest Electronic supplementary material The online version of this article (doi:10.1007/s10973-017-6317-1) contains supplementary material, which is available to authorized users. & Vladimir Logvinenko val@niic.nsc.ru 1 Nikolaev Institute of Inorganic Chemistry, Siberian Branch of Russian Academy of Sciences, Ac. Lavrentyev Ave 3, Novosibirsk, Russia 630090 2 Novosibirsk State University, Pirogova St 2, Novosibirsk, Russia 630090 123 J Therm Anal Calorim DOI 10.1007/s10973-017-6317-1