Anion-directed synthesis of metal-organic frameworks based on 2-picolinate Cu(II) complexes:: A ferromagnetic alternating chain and two unprecedented ferromagnetic fish backbone chains

被引:106
作者
Biswas, Chaitali
Mukherjee, Pampa
Drew, Michael G. B.
Gomez-Garcia, Carlos J.
Clemente-Juan, Juan M.
Ghosh, Ashutosh
机构
[1] Univ Valencia, ICMol, Valencia 46980, Spain
[2] Univ Calcutta, Univ Coll Sci, Dept Chem, Kolkata 700009, W Bengal, India
[3] Univ Reading, Sch Chem, Reading RG6 6AD, Berks, England
[4] FGUV, Balashikha, Russia
关键词
D O I
10.1021/ic701440x
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
Three new polynuclear copper(II) complexes of 2-picolinic acid (Hpic), {[Cu-2(pic)(3)(H2O)]ClO4}(n) (1), {[Cu-2(pic)(3)(H2O)]BF4}(n) (2), and [Cu-2(pic)3(H2O)(2)(NO3)](n) (3), have been synthesized by reaction of the "metalloligand" [Cu-(pic)(2)] with the corresponding copper(II) salts. The compounds are characterized by single-crystal X-ray diffraction analyses and variable-temperature magnetic measurements. Compounds 1 and 2 are isomorphous and crystallize in the triclinic system with space group P (1) over bar, while 3 crystallizes in the monoclinic system with space group P2(1)/n. The structural analyses reveal that complexes 1 and 2 are constructed by "fish backbone" chains through syn-anti (equatorial-equatorial) carboxylate bridges, which are linked to one another by syn-anti (equatorial-axial) carboxylate bridges, giving rise to a rectangular grid-like two-dimensional net. Complex 3 is formed by alternating chains of syn-anti carboxylate-bridged copper(II) atoms, which are linked together by strong H bonds involving coordinated nitrate ions and water molecules and uncoordinated oxygen atoms from carboxylate groups. The different coordination ability of the anions along with their involvement in the H-bonding network seems to be responsible for the difference in the final polymeric structures. Variable-temperature (2-300 K) magnetic susceptibility measurement shows the presence of weak ferromagnetic coupling for all three complexes that have been fitted with a fish backbone model developed for 1 and 2 (J = 1.74 and 0.99 cm(-1); J' = 0.19 and 0.25 cm(-1), respectively) and an alternating chain model for 3 (J = 1.19 cm(-1) and J' = 1.19 cm(-1)).
引用
收藏
页码:10771 / 10780
页数:10
相关论文
共 53 条
[1]   SYNTHESIS, STRUCTURE, AND SPECTROSCOPIC PROPERTIES OF COPPER(II) COMPOUNDS CONTAINING NITROGEN SULFUR DONOR LIGANDS - THE CRYSTAL AND MOLECULAR-STRUCTURE OF AQUA[1,7-BIS(N-METHYLBENZIMIDAZOL-2'-YL)-2,6-DITHIAHEPTANE]COPPER(II) PERCHLORATE [J].
ADDISON, AW ;
RAO, TN ;
REEDIJK, J ;
VANRIJN, J ;
VERSCHOOR, GC .
JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 1984, (07) :1349-1356
[2]  
[Anonymous], 2005, ABSPACK
[3]   DISCREPANCY BETWEEN THE STRUCTURAL AND MAGNETIC DIMENSIONALITY IN THE (MU-TEREPHTHALATO)BIS[(DIETHYLENETRIAMINE)CU(II)]PERCHLORATE COMPLEX [J].
BAKALBASSIS, E ;
TSIPIS, C ;
BOZOPOULOS, A ;
DREISSIG, W ;
HARTL, H ;
MROZINSKI, J .
INORGANICA CHIMICA ACTA, 1991, 186 (01) :113-118
[4]   Combined effects of diamines and carboxylate bridges on structural and magnetic properties of a series of polynuclear copper(II) complexes with 1,1-cyclobutanedicarboxylic acid [J].
Baldoma, Raul ;
Monfort, Montserrat ;
Ribas, Joan ;
Solans, Xavier ;
Maestro, Miguel A. .
INORGANIC CHEMISTRY, 2006, 45 (20) :8144-8155
[5]   High-nuclearity magnetic clusters:: Generalized spin Hamiltonian and its use for the calculation of the energy levels, bulk magnetic properties, and inelastic neutron scattering spectra [J].
Borrás-Almenar, JJ ;
Clemente-Juan, JM ;
Coronado, E ;
Tsukerblat, BS .
INORGANIC CHEMISTRY, 1999, 38 (26) :6081-6088
[6]   MAGPACK1 a package to calculate the energy levels, bulk magnetic properties, and inelastic neutron scattering spectra of high nuclearity spin clusters [J].
Borrás-Almenar, JJ ;
Clemente-Juan, JM ;
Coronado, E ;
Tsukerblat, BS .
JOURNAL OF COMPUTATIONAL CHEMISTRY, 2001, 22 (09) :985-991
[7]   Syntheses and characterizations of two lanthanide(III)-copper(II) coordination polymers constructed by pyridine-2,6-dicarboxylic acid [J].
Cai, YP ;
Su, CY ;
Li, GB ;
Mao, ZW ;
Zhang, C ;
Xu, AW ;
Kang, BS .
INORGANICA CHIMICA ACTA, 2005, 358 (04) :1298-1304
[8]   MAGNETOCHEMISTRY OF COPPER(II) - EXCHANGE INTERACTIONS IN CATENATED [CU(NH3)2(CH3COO)BR] [J].
CARLIN, RL ;
KOPINGA, K ;
KAHN, O ;
VERDAGUER, M .
INORGANIC CHEMISTRY, 1986, 25 (11) :1786-1789
[9]   STRUCTURE AND MAGNETIC-PROPERTIES OF A SYN-ANTI CARBOXYLATE BRIDGED LINEAR TRINUCLEAR COPPER(II) COMPLEX WITH FERROMAGNETIC EXCHANGE INTERACTION [J].
COLACIO, E ;
DOMINGUEZVERA, JM ;
KIVEKAS, R ;
MORENO, JM ;
ROMEROSA, A ;
RUIZ, J .
INORGANICA CHIMICA ACTA, 1993, 212 (1-2) :115-121
[10]   A QUASI-TETRAHEDRAL CU-4 CLUSTER WITH SYN-ANTI BRIDGING CARBOXYLATE GROUPS - CRYSTAL AND MOLECULAR-STRUCTURE AND MAGNETIC-PROPERTIES [J].
COLACIO, E ;
COSTES, JP ;
KIVEKAS, R ;
LAURENT, JP ;
RUIZ, J .
INORGANIC CHEMISTRY, 1990, 29 (21) :4240-4246