Self-assembly, binding ability and magnetic properties of dicopper(II) pyrazolenophanes

被引:6
作者
Barros, Wdeson P. [1 ,3 ]
Luisa Calatayud, M. [1 ]
Lloret, Francesc [1 ]
Julve, Miguel [1 ]
Marino, Nadia [5 ,6 ]
De Munno, Giovanni [5 ]
Stumpf, Humberto O. [4 ]
Ruiz-Garcia, Rafael [1 ,2 ]
Castro, Isabel [1 ]
机构
[1] Univ Valencia, Inst Ciencia Mol ICMol, E-46980 Valencia, Spain
[2] FGUV, Valencia, Spain
[3] Univ Estadual Campinas, Inst Quim, Campinas, SP, Brazil
[4] Univ Fed Minas Gerais, Dept Quim ICEx, BR-31270901 Belo Horizonte, MG, Brazil
[5] Univ Calabria, Dipartimento Chim & Tecnol Chim CTC, I-87036 Cosenza, Italy
[6] Syracuse Univ, Dept Chem, Syracuse, NY 13244 USA
来源
CRYSTENGCOMM | 2016年 / 18卷 / 03期
关键词
METAL PYRAZOLATE POLYMERS; COORDINATION POLYMERS; THEORETICAL PREDICTIONS; COPPER(II) COMPLEXES; MOLECULAR-STRUCTURE; SPIN POLARIZATION; BRIDGING LIGANDS; RATIONAL DESIGN; OPEN-FRAMEWORK; SOLID-STATE;
D O I
10.1039/c5ce02058a
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
A novel series of dinuclear copper(II) pyrazolenophanes of the formula [Cu-2(mu-4-Mepz)(2)(mu-ClO4)(ClO4)(bpm)(2)] (1), [Cu-2(mu-pz)(2)(mu-H2O)(ClO4)(4,7-Me(2)phen)(2)]ClO4 center dot H2O center dot CH3CN (2), [Cu-2(mu-pz)(2)(mu-H2O)(ClO4)(3/2)(H2O)(1/2)(phen)(2)](2)[Cu-2(mu-pz)(2)(mu-ClO4)(ClO4)(2)(phen)(2)]center dot 8H(2)O (3), and [Cu-2(mu-pz)(2)(CH3CN)(2)(3,4,7,8-Me(4)phen)(2)](ClO4)(2) (4) (Hpz = pyrazole, H-4-Mepz = 4-methylpyrazole, bpm = 2,2'-bipyrimidine, phen = 1,10-phenanthroline, 4,7-Me(2)phen = 4,7-dimethyl-1,10-phenanthroline, and 3,4,7,8-Me(4)phen = 3,4,7,8-tetramethyl-1,10-phenanthroline) have been synthesized and magneto-structurally investigated. The crystal structures of 1-4 contain bis(pyrazolate)(perchlorate)-(1 and 3), bis(pyrazolate)(aqua)-(2 and 3), or bis(pyrazolate)-bridged (4) dicopper(II) entities of the metallacyclophane-type with bpm (1), 4,7-Me(2)phen (2), phen (3), and 3,4,7,8-Me(4)phen (4) as blocking bidentate ligands. All of them exhibit a saddle conformation with an overall not planar but bent, six-membered Cu-(N-N')(2)-Cu metallacyclic core with relatively short intermetallic distances across the bis(pyrazolate)(perchlorate) [r = 3.3076(5) (1) and 3.382(1) angstrom (3)], bis(pyrazolate)(aqua) [r = 3.383(1) (2) and 3.357(1) angstrom (3)], and bis(pyrazolate) bridges [r = 3.098(1) angstrom (4)]. The analyses of the variable-temperature magnetic susceptibility of 1-4 reveal the occurrence of a moderately strong antiferromagnetic coupling across the bis(pyrazolate)(perchlorate) [-J = 228 (1) and 193 cm(-1) (3)], bis(pyrazolate)(aqua) [-J = 189 (2) and 221 cm(-1) (3)], and bis(pyrazolate) bridges [-J = 197 cm(-1) (4)] (the spin Hamiltonian being defined as H = -JS(1).S-2 with S-1 = S-2 = S-Cu = 1/2).
引用
收藏
页码:437 / 449
页数:13
相关论文
共 105 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]   ANISOTROPIC EXCHANGE IN DINUCLEAR COMPLEXES WITH POLYATOMIC BRIDGES .2. CRYSTAL AND MOLECULAR-STRUCTURE AND ELECTRON-PARAMAGNETIC-RES SPECTRA OF TETRAPHENYLPHOSPHONIUM BIS(MU-PYRAZOLATO)BIS[DIHYDROBIS(1-PYRAZOLYL)BORATO](MU-CHLORO)DICUPRATE(II) - MAGNETO STRUCTURAL CORRELATIONS IN BIS(MU-PYRAZOLATO)-BRIDGED COPPER(II) COMPLEXESO [J].
AJO, D ;
BENCINI, A ;
MANI, F .
INORGANIC CHEMISTRY, 1988, 27 (14) :2437-2444
[3]   Catechol imine ligands:: from helicates to supramolecular tetrahedra [J].
Albrecht, M ;
Ingo, JA ;
Fröhlich, R .
CHEMICAL COMMUNICATIONS, 2005, (02) :157-165
[4]   Dicatechol ligands: novel building-blocks for metallo-supramolecular chemistry [J].
Albrecht, M .
CHEMICAL SOCIETY REVIEWS, 1998, 27 (04) :281-287
[5]  
[Anonymous], 2000, SADABS VERS 2 03
[6]  
[Anonymous], 2003, SAINT VERS 6 45
[7]  
[Anonymous], 1991, MODERN MOL PHOTOCHEM
[8]  
[Anonymous], 2006, DIAMOND 3 1B CRYSTAL
[9]   Luminescent and redox-active polynuclear transition metal complexes [J].
Balzani, V ;
Juris, A ;
Venturi, M ;
Campagna, S ;
Serroni, S .
CHEMICAL REVIEWS, 1996, 96 (02) :759-833
[10]   Vertex-, face-, point-, Schlafli-, and Delaney-symbols in nets, polyhedra and tilings: recommended terminology [J].
Blatov, V. A. ;
O'Keeffe, M. ;
Proserpio, D. M. .
CRYSTENGCOMM, 2010, 12 (01) :44-48