TY - JOUR
T1 - Changing Single-Molecule Magnet Properties of a Windmill-Like Distorted Terbium(III) α-Butoxy-Substituted Phthalocyaninato Double-Decker Complex by Protonation/Deprotonation
AU - Horii, Yoji
AU - Horie, Yusuke
AU - Katoh, Keiichi
AU - Breedlove, Brian K.
AU - Yamashita, Masahiro
N1 - Funding Information:
This work was financially supported by JSPS KAKENHI Grant Nos. JP20225003, JP15K05467, JP24750119, JP14J02656 Tohoku University Molecule & Material Synthesis Platform in Nanotechnology Platform Project, and CREST, JST (JPMJCR12L3), Japan.
Funding Information:
This work was financially supported by JSPS KAKENHI Grant Nos. JP20225003, JP15K05467, JP24750119, JP14J02656, Tohoku University Molecule & Material Synthesis Platform in Nanotechnology Platform Project, and CREST, JST (JPMJCR12L3), Japan.
Publisher Copyright:
© 2017 American Chemical Society.
PY - 2018/1/16
Y1 - 2018/1/16
N2 - Synthesis, structures, and magnetic properties of α-butoxy-substituted phthalocyaninato double-decker complexes Tb(α-obPc)2 (1-) (α-obPc: dianion of 1,4,8,11,15,18,22,25-octa(n-butoxy)phthalocyaninato) with protonated (1H), deprotonated (1[HDBU]), and diprotonated forms (1H2+) are discussed. X-ray analysis was used to confirm the position of the proton in 1H, and it was revealed that the protonation induced asymmetric distortion in 1H. In contrast, 1[HDBU] was distorted in a highly symmetric windmill-like fashion. 1H is arranged in a slipped column array in the crystal packing, whereas 1[HDBU] is arranged in a one-dimensional fashion, in which the magnetic easy axes of 1[HDBU] lie along the same line. From direct-current (dc) magnetic measurements, ferromagnetic Tb-Tb interactions occur in both 1H and 1[HDBU], and magnetic hysteresis was observed. However, the area of the magnetic hysteresis in 1[HDBU] is larger than that in 1H, meaning that magnetic relaxation time (τ) is longer in 1[HDBU]. In addition, the results of alternating-current magnetic measurements in a zero dc magnetic field indicate that τ of 1[HDBU] is longer as compared to 1H. In other words, protonation/deprotonation affects not only the molecular structures and crystal packing but also the single-molecule magnet properties.
AB - Synthesis, structures, and magnetic properties of α-butoxy-substituted phthalocyaninato double-decker complexes Tb(α-obPc)2 (1-) (α-obPc: dianion of 1,4,8,11,15,18,22,25-octa(n-butoxy)phthalocyaninato) with protonated (1H), deprotonated (1[HDBU]), and diprotonated forms (1H2+) are discussed. X-ray analysis was used to confirm the position of the proton in 1H, and it was revealed that the protonation induced asymmetric distortion in 1H. In contrast, 1[HDBU] was distorted in a highly symmetric windmill-like fashion. 1H is arranged in a slipped column array in the crystal packing, whereas 1[HDBU] is arranged in a one-dimensional fashion, in which the magnetic easy axes of 1[HDBU] lie along the same line. From direct-current (dc) magnetic measurements, ferromagnetic Tb-Tb interactions occur in both 1H and 1[HDBU], and magnetic hysteresis was observed. However, the area of the magnetic hysteresis in 1[HDBU] is larger than that in 1H, meaning that magnetic relaxation time (τ) is longer in 1[HDBU]. In addition, the results of alternating-current magnetic measurements in a zero dc magnetic field indicate that τ of 1[HDBU] is longer as compared to 1H. In other words, protonation/deprotonation affects not only the molecular structures and crystal packing but also the single-molecule magnet properties.
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U2 - 10.1021/acs.inorgchem.7b02124
DO - 10.1021/acs.inorgchem.7b02124
M3 - Article
C2 - 29027796
AN - SCOPUS:85040831427
SN - 0020-1669
VL - 57
SP - 565
EP - 574
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 2
ER -