Guest Modulation of Spin‐Crossover Transition Temperature in a Porous Iron(II) Metal–Organic Framework: Experimental and Periodic DFT Studies |
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| Authors: | Dr. Daniel Aravena Zulema Arcís Castillo Prof. Dr. M. Carmen Muñoz Dr. Ana B. Gaspar Dr. Ko Yoneda Dr. Ryo Ohtani Dr. Akio Mishima Prof. Dr. Susumu Kitagawa Prof. Dr. Masaaki Ohba Prof. Dr. José Antonio Real Prof. Dr. Eliseo Ruiz |
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| Affiliation: | 1. Departament de Química Inorgànica and Institut de Recerca de Química Teòrica i Computacional, Universitat de Barcelona, Barcelona 08028 (Spain);2. Instituto de Ciencia Molecular (ICMol), Universidad de Valencia, 46980 Paterna, Valencia (Spain);3. Departamento de Física Aplicada, Universitat Politècnica de València, 46022, Valencia (Spain);4. Faculty of Science and Engineering, Saga University, Saga 840‐8502 (Japan);5. Kyoto University, Katsura, Nishikyo‐ku, Kyoto615‐8581 (Japan);6. Department of Chemistry, Faculty of Science, Kyushu University, Hakozaki, Higashi‐ku, Fukuoka 812‐8581 (Japan);7. Institute for Integrated Cell‐Material Sciences (iCeMS), Kyoto University, Yoshida, Sakyo‐ku, Kyoto 606‐8501 (Japan) |
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| Abstract: | The synthesis, structure, and magnetic properties of three clathrate derivatives of the spin‐crossover porous coordination polymer {Fe(pyrazine)[Pt(CN)4]} ( 1 ) with five‐membered aromatic molecules furan, pyrrole, and thiophene is reported. The three derivatives have a cooperative spin‐crossover transition with hysteresis loops 14–29 K wide and average critical temperatures Tc=201 K ( 1?fur ), 167 K ( 1?pyr ), and 114.6 K ( 1?thio ) well below that of the parent compound 1 (Tc=295 K), confirming stabilization of the HS state. The transition is complete and takes place in two steps for 1?fur , while 1?pyr and 1?thio show 50 % spin transition. For 1?fur the transformation between the HS and IS (middle of the plateau) phases occurs concomitantly with a crystallographic phase transition between the tetragonal space groups P4/mmm and I4/mmm, respectively. The latter space group is retained in the subsequent transformation involving the IS and the LS phases. 1?pyr and 1?thio display the tetragonal P4/mmm and orthorhombic Fmmm space groups, respectively, in both HS and IM phases. Periodic calculations using density functional methods for 1?fur , 1?pyr , 1?thio , and previously reported derivatives 1?CS2 , 1?I, 1?bz (benzene), and 1?pz (pyrazine) have been carried out to investigate the electronic structure and nature of the host–guest interactions as well as their relationship with the changes in the LS–HS transition temperatures of 1?Guest . Geometry‐optimized lattice parameters and bond distances in the empty host 1 and 1?Guest clathrates are in general agreement with the X‐ray diffraction data. The concordance between the theoretical results and the experimental data also comprises the guest molecule orientation inside the host and intermolecular distances. Furthermore, a general correlation between experimental Tc and calculated LS–HS electronic energy gap was observed. Finally, specific host–guest interactions were studied through interaction energy calculations and crystal orbital displacement (COD) curve analysis. |
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| Keywords: | density functional calculations Hofmann clathrates magnetic properties metal– organic frameworks spin‐crossover compounds |
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