TY - JOUR
T1 - Cation Exchange in Dynamic 3D Porous Magnets
T2 - Improvement of the Physical Properties
AU - Grancha, Thais
AU - Acosta, Alvaro
AU - Cano, Joan
AU - Ferrando-Soria, Jesús
AU - Seoane, Beatriz
AU - Gascon, Jorge
AU - Pasán, Jorge
AU - Armentano, Donatella
AU - Pardo, Emilio
N1 - Publisher Copyright:
© 2015 American Chemical Society.
PY - 2015/10/22
Y1 - 2015/10/22
N2 - We report two novel three-dimensional porous coordination polymers (PCPs) of formulas Li4{Mn4[Cu2(Me3mpba)2]3}·68H2O (2) and K4{Mn4[Cu2(Me3mpba)2]3}·69H2O (3) obtained - via alkali cation exchange in a single-crystal to single-crystal process - from the earlier reported anionic manganese(II)-copper(II) PCP of formula Na4{Mn4[Cu2(Me3mpba)2]3}·60H2O (1) [Me3mpba4- = N,N′-2,4,6-trimethyl-1,3-phenylenebis(oxamate)]. This postsynthetic process succeeds where the direct synthesis in solution from the corresponding building blocks fails and affords significantly more robust PCPs with enhanced magnetic properties [long-range 3D magnetic ordering temperatures for the dehydrated phases (1′-3′) of 2.0 (1′), 12.0 (2′), and 20.0 K (3′)]. Changes in the adsorptive properties upon postsynthetic exchange suggest that the nature, electrostatic properties, mobility, and location of the cations within the framework are crucial for the enhanced structural stability. Overall, these results further confirm the potential of postsynthetic methods (including cation exchange) to obtain PCPs with novel or enhanced physical properties while maintaining unaltered their open-framework structures.
AB - We report two novel three-dimensional porous coordination polymers (PCPs) of formulas Li4{Mn4[Cu2(Me3mpba)2]3}·68H2O (2) and K4{Mn4[Cu2(Me3mpba)2]3}·69H2O (3) obtained - via alkali cation exchange in a single-crystal to single-crystal process - from the earlier reported anionic manganese(II)-copper(II) PCP of formula Na4{Mn4[Cu2(Me3mpba)2]3}·60H2O (1) [Me3mpba4- = N,N′-2,4,6-trimethyl-1,3-phenylenebis(oxamate)]. This postsynthetic process succeeds where the direct synthesis in solution from the corresponding building blocks fails and affords significantly more robust PCPs with enhanced magnetic properties [long-range 3D magnetic ordering temperatures for the dehydrated phases (1′-3′) of 2.0 (1′), 12.0 (2′), and 20.0 K (3′)]. Changes in the adsorptive properties upon postsynthetic exchange suggest that the nature, electrostatic properties, mobility, and location of the cations within the framework are crucial for the enhanced structural stability. Overall, these results further confirm the potential of postsynthetic methods (including cation exchange) to obtain PCPs with novel or enhanced physical properties while maintaining unaltered their open-framework structures.
UR - http://www.scopus.com/inward/record.url?scp=84947601767&partnerID=8YFLogxK
U2 - 10.1021/acs.inorgchem.5b01854
DO - 10.1021/acs.inorgchem.5b01854
M3 - Article
AN - SCOPUS:84947601767
SN - 0020-1669
VL - 54
SP - 10834
EP - 10840
JO - Inorganic chemistry
JF - Inorganic chemistry
IS - 22
ER -