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Hydrogen‐Bonded Polyrotaxane Cation Structure in Nickel Dithiolate Anion Radical Salts: Ferromagnetic and Semiconducting Behavior Associated with Structural Phase Transition
Author(s) -
Shirakawa Yuki,
Takahashi Kiyonori,
Sato Hiroyasu,
Hoshino Norihisa,
Anetai Hayato,
Noro Shinichiro,
Akutagawa Tomoyuki,
Nakamura Takayoshi
Publication year - 2019
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201806230
Subject(s) - crystallography , crystal structure , hydrogen bond , crown ether , chemistry , crystal (programming language) , phase (matter) , phenylene , side chain , nickel , ion , materials science , molecule , organic chemistry , polymer , computer science , programming language
The pseudo‐polyrotaxane structure of [(H‐bpy + )‐ (DB‐24‐crown‐8)] ∞ (H‐bpy + = monoprotonated 4,4‐bipyridinium; DB‐24‐crown‐8 = dibenzo‐24‐crown‐8) has been incorporated into the anion radical salt [Ni(dmit) 2 ] − (dmit 2− = 1,3‐dithiole‐2‐thione‐4,5‐dithiolate). (H‐bpy + )(DB‐24‐crown‐8)[Ni(dmit) 2 ] − crystallized as two polymorphs, crystals 1 and 2 . Crystal 1 was found to have a lower density and looser packing structure in which H‐bpy + forms a one‐dimensional hydrogen‐bonding chain that passes though the crown ether ring of DB‐24‐crown‐8. DB‐24‐crown‐8 adopts a U‐shaped conformation in which two phenylene rings sandwich one of the pyridyl rings of H‐bpy + to stabilize the structure. The [Ni(dmit) 2 ] − anions are arranged in a layer parallel to the (10) plane with uniform side‐by‐side interactions. A structural phase transition was observed at 235 K, accompanied by ordering of the polyrotaxane structure. In crystal 1 , at 173 K, H‐bpy + is twisted around the central C−C bond, which perturbs the arrangement of [Ni(dmit) 2 ] − through short C−H⋅⋅⋅S contacts. As a result, the semiconducting behavior, with an activation energy of 0.21 eV, becomes insulating below 235 K. The crystal exhibits ferromagnetic interactions because of the weak side‐by‐side interactions between [Ni(dmit) 2 ] − anions. Crystal 2 has a similar pseudo‐polyrotaxane structure but showed no phase transition. This suggests that the looser crystal packing in crystal 1 induces the structural change of the pseudo‐polyrotaxane, perturbing the electron system of [Ni(dmit) 2 ] − .