title: The key role of vibrational entropy in the phase transitions of dithiazolyl-based bistable magnetic materials.
abstract: The neutral radical 1,3,5-trithia-2,4,6-triazapentalenyl (TTTA) is a prototype of molecule-based bistable materials. TTTA crystals undergo a first-order phase transition between their low-temperature diamagnetic and high-temperature paramagnetic phases, with a large hysteresis loop that encompasses room temperature. Here, based on ab initio molecular dynamics simulations and new X-ray measurements, we uncover that the regular stacking motif of the high-temperature polymorph is the result of a fast intra-stack pair-exchange dynamics, whereby TTTA radicals continually exchange the adjacent TTTA neighbour (upper or lower) with which they form an eclipsed dimer. Such unique dynamics, observed in the paramagnetic phase within the whole hysteresis loop, is the origin of a significant vibrational entropic gain in the low-temperature to high-temperature transition and thereby it plays a key role in driving the phase transition. This finding provides a new key concept that needs to be explored for the rational design of novel molecule-based bistable magnetic materials.
authors.affiliation: Departament de Química Física and IQTCUB, Universitat de Barcelona, Avinguda Diagonal 645, 08028 Barcelona, Spain.
authors.forename: Sergi
authors.initials: S
authors.lastname: Vela
authors.affiliation: Departament de Química Física and IQTCUB, Universitat de Barcelona, Avinguda Diagonal 645, 08028 Barcelona, Spain.
authors.forename: Fernando
authors.initials: F
authors.lastname: Mota
authors.affiliation: Departament de Química Física and IQTCUB, Universitat de Barcelona, Avinguda Diagonal 645, 08028 Barcelona, Spain.
authors.forename: Mercè
authors.initials: M
authors.lastname: Deumal
authors.affiliation: 1] Department of Nanomaterials Science, Chiba University, 1-33, Yayoi-cho, Inage-ku, Chiba 263-8522, Japan [2] JST-CREST, Nagoya University, Furo-cho, Chikusa-ku, Nagoya 464-8602, Japan.
authors.forename: Rie
authors.initials: R
authors.lastname: Suizu
authors.affiliation: Department of Chemistry, Research Center for Materials Science, Nagoya University, Furo-cho, Chikusa-ku, Nagoya 464-8602, Japan.
authors.forename: Yoshiaki
authors.initials: Y
authors.lastname: Shuku
authors.affiliation: Department of Chemistry, Research Center for Materials Science, Nagoya University, Furo-cho, Chikusa-ku, Nagoya 464-8602, Japan.
authors.forename: Asato
authors.initials: A
authors.lastname: Mizuno
authors.affiliation: 1] JST-CREST, Nagoya University, Furo-cho, Chikusa-ku, Nagoya 464-8602, Japan [2] Department of Chemistry, Research Center for Materials Science, Nagoya University, Furo-cho, Chikusa-ku, Nagoya 464-8602, Japan.
authors.forename: Kunio
authors.initials: K
authors.lastname: Awaga
authors.affiliation: Center for Computational Science and E-Systems, Japan Atomic Energy Agency, 5-1-5, Kashiwanoha, Kashiwa, Chiba 277-8587, Japan.
authors.forename: Motoyuki
authors.initials: M
authors.lastname: Shiga
authors.affiliation: Departament de Química Física and IQTCUB, Universitat de Barcelona, Avinguda Diagonal 645, 08028 Barcelona, Spain.
authors.forename: Juan J
authors.initials: JJ
authors.lastname: Novoa
authors.affiliation: Departament de Química Física and IQTCUB, Universitat de Barcelona, Avinguda Diagonal 645, 08028 Barcelona, Spain.
authors.forename: Jordi
authors.initials: J
authors.lastname: Ribas-Arino