TY - JOUR
T1 - A Blockwall-Type Layered Bis(dithiolato)nickelate Radical Salt Exhibiting High- and Two-Dimensional Antiferromagnetic Coupling Feature
AU - Yao, Wan Wan
AU - Qian, Yin
AU - Chen, Xuan Rong
AU - Ren, Xiao Ming
N1 - Publisher Copyright:
© 2021 SIOC, CAS, Shanghai & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
PY - 2022/4/1
Y1 - 2022/4/1
N2 - The family of [M(dmit)2]- salts (dmit2- = 2-thioxo-1,3-dithiole-4,5-dithiolate; M = Ni, Pd and Pt) generally show novel magnetic, electric, magnetoelectric and photoelectric properties. Herein, a blockwall-type layered [Me3S][Ni(dmit)2] radical salt (1; Me3S+ = trimethylsulfonium) was prepared and characterized by microanalysis, IR spectroscopy, thermal analysis, powder and single crystal X-ray diffraction techniques. Salt 1 crystalizes in triclinic space group P-1, with two pairs of [Ni(dmit)2]- and Me3S+ ions in an asymmetric unit. The anions form blockwall-type monolayer, being parallel to crystallographic (0 1 1) plane, and the cations are accommodated in the spaces of anion monolayer. Salt 1 features a two-dimensional S = ½ antiferromagnetic (AFM) spin system with θ = -97.8(1) K and a semiconductor with σ ≈ 10-4 S·cm-1 and activation energy Ea = 0.24(1) eV in 308—368 K. 1 shows two-step dielectric relaxations ranged from 173—373 K and 1—107 Hz for the dipole motions of two different polar cations. Most importantly, the dielectric constant of 1 reaches to ~17, with high-κ nature. This study suggests the possibility of achieving high-κ materials by introducing polar and low rotation barrier components into van der Waals crystal and high-κ [Ni(dmit)2]--based electrode materials for applications in supercapacitors.
AB - The family of [M(dmit)2]- salts (dmit2- = 2-thioxo-1,3-dithiole-4,5-dithiolate; M = Ni, Pd and Pt) generally show novel magnetic, electric, magnetoelectric and photoelectric properties. Herein, a blockwall-type layered [Me3S][Ni(dmit)2] radical salt (1; Me3S+ = trimethylsulfonium) was prepared and characterized by microanalysis, IR spectroscopy, thermal analysis, powder and single crystal X-ray diffraction techniques. Salt 1 crystalizes in triclinic space group P-1, with two pairs of [Ni(dmit)2]- and Me3S+ ions in an asymmetric unit. The anions form blockwall-type monolayer, being parallel to crystallographic (0 1 1) plane, and the cations are accommodated in the spaces of anion monolayer. Salt 1 features a two-dimensional S = ½ antiferromagnetic (AFM) spin system with θ = -97.8(1) K and a semiconductor with σ ≈ 10-4 S·cm-1 and activation energy Ea = 0.24(1) eV in 308—368 K. 1 shows two-step dielectric relaxations ranged from 173—373 K and 1—107 Hz for the dipole motions of two different polar cations. Most importantly, the dielectric constant of 1 reaches to ~17, with high-κ nature. This study suggests the possibility of achieving high-κ materials by introducing polar and low rotation barrier components into van der Waals crystal and high-κ [Ni(dmit)2]--based electrode materials for applications in supercapacitors.
KW - Magnetic properties
KW - Metal-dithiolene complex
KW - Radical ions
KW - Semiconductors
KW - high-κ
UR - http://www.scopus.com/inward/record.url?scp=85123484655&partnerID=8YFLogxK
U2 - 10.1002/cjoc.202100710
DO - 10.1002/cjoc.202100710
M3 - 文章
AN - SCOPUS:85123484655
SN - 1001-604X
VL - 40
SP - 794
EP - 800
JO - Chinese Journal of Chemistry
JF - Chinese Journal of Chemistry
IS - 7
ER -