TY - JOUR
T1 - Unprecedented (4,6)-connected net with mixed-valence M2 IIMIII trinuclear and M6II hexanuclear clusters (M = Ni, Co)
T2 - Syntheses, crystal structures, and magnetic properties
AU - Zhai, Lu
AU - Yang, Zhu Xi
AU - Zhang, Wen Wei
AU - Zuo, Jing Lin
AU - Ren, Xiao Ming
N1 - Publisher Copyright:
© 2017 American Chemical Society.
PY - 2017/10/4
Y1 - 2017/10/4
N2 - Two new cluster-based metal-organic frameworks (MOFs), {(M3OH)2[(M6O(OH)2(H2O)2]1.5(EBTC)6} solvent (M = Ni and Co for 1 and 2, respectively), have been synthesized using a solvothermal reaction, where H4EBTC represents 1, 1′-ethynebenzene-3, 3′, 5, ′-tetracarboxylic acid. The isostructural 1 and 2 crystallize in the hexagonal space group P6/mmm, containing class III mixed-valence Ni2 IINiIII/Co2 IICoIII trinuclear and Ni6 II/Co6 II hexanuclear secondary building units (SBUs). Both SBUs possess the perfectly planar μ3-O2- and μ4-O2- bridging mode, respectively. In 1 and 2, two trinuclear and three hexanuclear clusters form a cage with the dimensions of ca. 5.0 × 5.0 × 7.8 Å3, which align into a bamboo-like structure through sharing the trinuclear clusters along the c-axis, and form a honeycomb-like structure via sharing the hexanuclear clusters on the plane parallel to the crystallographic (001) plane. In addition, the magnetic properties have been further investigated for two MOFs, disclosing that the weakly antiferromagnetic couplings dominate between the metal ions and no valence ordering occurs even at 2 K.
AB - Two new cluster-based metal-organic frameworks (MOFs), {(M3OH)2[(M6O(OH)2(H2O)2]1.5(EBTC)6} solvent (M = Ni and Co for 1 and 2, respectively), have been synthesized using a solvothermal reaction, where H4EBTC represents 1, 1′-ethynebenzene-3, 3′, 5, ′-tetracarboxylic acid. The isostructural 1 and 2 crystallize in the hexagonal space group P6/mmm, containing class III mixed-valence Ni2 IINiIII/Co2 IICoIII trinuclear and Ni6 II/Co6 II hexanuclear secondary building units (SBUs). Both SBUs possess the perfectly planar μ3-O2- and μ4-O2- bridging mode, respectively. In 1 and 2, two trinuclear and three hexanuclear clusters form a cage with the dimensions of ca. 5.0 × 5.0 × 7.8 Å3, which align into a bamboo-like structure through sharing the trinuclear clusters along the c-axis, and form a honeycomb-like structure via sharing the hexanuclear clusters on the plane parallel to the crystallographic (001) plane. In addition, the magnetic properties have been further investigated for two MOFs, disclosing that the weakly antiferromagnetic couplings dominate between the metal ions and no valence ordering occurs even at 2 K.
UR - http://www.scopus.com/inward/record.url?scp=85042476549&partnerID=8YFLogxK
U2 - 10.1021/acs.cgd.7b00795
DO - 10.1021/acs.cgd.7b00795
M3 - 文章
AN - SCOPUS:85042476549
SN - 1528-7483
VL - 17
SP - 5263
EP - 5268
JO - Crystal Growth and Design
JF - Crystal Growth and Design
IS - 10
ER -