TY - JOUR
T1 - Observation of strongly antiferromagnetic exchange interactions in four quasi-one-dimensional bis(maleonitriledithiolato) palladate monoanion spin systems
T2 - An insight from DFT calculation
AU - Zhang, Hui
AU - Chen, Xuan Rong
AU - Ren, Xiao Ming
AU - Meng, Qing Jin
PY - 2011/12
Y1 - 2011/12
N2 - Four quasi-one-dimensional (quasi-1D) compounds consist of bis (maleonitriledithiolato)palladate monoanions ([Pd(mnt)2]-) with benzylpyridinium derivatives (R-BzPy+, where R represents the substituent in the para-site of the phenyl ring; R=Cl, Br, I and NO2 for 1~4, respectively), which show similar stacking structures to the [Ni(mnt)2]- analogues. The [Pd(mnt)2]- and R-BzPy+ ions form the segregated stacks, each stack is surrounded by four counterion stacks. In comparison of [Pd(mnt)2]- with [Ni(mnt)2]- analogues, the structural distinctions involving both anion and cation stacks are regular for [Ni(mnt)2]- series; while irregular for [Pd(mnt)2]- analogues at room temperature. The inter-plane distances are shorter in [Pd(mnt)2]- than those in [Ni(mnt)2]- stack. There exist strongly antiferromagnetic (AFM) interactions in [Pd(mnt)2]- stack, which magnetic exchange constants are evaluated via broken-symmetry approach in DFT framework, and the calculated results at svwn/lanl2dz and bpw91/lanl2dz levels are parallel to the experimental results, disclosing that the strongly AFM interactions is due to larger overlap of π-type frontier molecular orbitals.
AB - Four quasi-one-dimensional (quasi-1D) compounds consist of bis (maleonitriledithiolato)palladate monoanions ([Pd(mnt)2]-) with benzylpyridinium derivatives (R-BzPy+, where R represents the substituent in the para-site of the phenyl ring; R=Cl, Br, I and NO2 for 1~4, respectively), which show similar stacking structures to the [Ni(mnt)2]- analogues. The [Pd(mnt)2]- and R-BzPy+ ions form the segregated stacks, each stack is surrounded by four counterion stacks. In comparison of [Pd(mnt)2]- with [Ni(mnt)2]- analogues, the structural distinctions involving both anion and cation stacks are regular for [Ni(mnt)2]- series; while irregular for [Pd(mnt)2]- analogues at room temperature. The inter-plane distances are shorter in [Pd(mnt)2]- than those in [Ni(mnt)2]- stack. There exist strongly antiferromagnetic (AFM) interactions in [Pd(mnt)2]- stack, which magnetic exchange constants are evaluated via broken-symmetry approach in DFT framework, and the calculated results at svwn/lanl2dz and bpw91/lanl2dz levels are parallel to the experimental results, disclosing that the strongly AFM interactions is due to larger overlap of π-type frontier molecular orbitals.
KW - Bis(maleonitriledithiolato)palladate monoanion
KW - Broken-symmetry
KW - Density functional theory
KW - Magnetic property
UR - http://www.scopus.com/inward/record.url?scp=82655183750&partnerID=8YFLogxK
M3 - 文章
AN - SCOPUS:82655183750
SN - 1001-4861
VL - 27
SP - 2464
EP - 2472
JO - Chinese Journal of Inorganic Chemistry
JF - Chinese Journal of Inorganic Chemistry
IS - 12
ER -