From achiral ligands to chiral coordination polymers: Spontaneous resolution, weak ferromagnetism, and topological ferrimagnetism

被引:536
作者
Gao, EQ
Yue, YF
Bai, SQ
He, Z
Yan, CH [1 ]
机构
[1] Peking Univ, State Key Lab Rare Earth Mat Chem & Applicat, Beijing 100871, Peoples R China
[2] Peking Univ, PKU HKU Joint Lab Rare Earth Mat & Bioingn Chem, Beijing 100871, Peoples R China
[3] Qufu Normal Univ, Dept Chem, Shandong 273165, Peoples R China
[4] E China Normal Univ, Shanghai Key Lab Green chem & chem Proc, Shanghai 200062, Peoples R China
关键词
D O I
10.1021/ja039104a
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Using the achiral diazine ligands bearing two bidentate pyridylimino groups as sources of conformational chirality, five azido-bridged coordination polymers are prepared and characterized crystallographically and magnetically. The chirality of the molecular units is induced by the coordination of the diazine ligands in a twisted chiral conformation. The use of L-1 (1,4-bis(2-pyridyl)-1-amino-2,3-diaza-1,3-butadiene) and L-2 (1,4-bis(2-pyridyl)-1,4-diamino-2,3-diaza-1,3-butadiene) induces spontaneous resolution, yielding conglomerates of chiral compounds [Mn-3(L-1)(2)(N-3)(6)](n) (1) and [Mn-2(L-2)(2)(N-3)(3)](n)(ClO4)(n)(.)nH(2)O (2), respectively, where triangular (1) or double helical (2) chiral units are connected into homochiral one-dimensional (1D) chains via single end-to-end (EE) azido bridges. The chains are stacked via hydrogen bonds in a homochiral fashion to yield chiral crystals. When L-3 (2,5-bis(2-pyridyl)-3,4-diaza-2,4-hexadiene) is employed, a partial spontaneous resolution occurs, where binuclear chiral units are interlinked into fishscale-like homochiral two-dimensional (2D) layers via single EE azido bridges. The layers are stacked in a heterochiral or homochiral fashion to yield simultaneously a racemic compound, [Mn-2(L-3)(N-3)(4)](n) (3a), and a conglomerate, [Mn-2(L-3)(N-3)(4)](n)(.)nMeOH (3b). On the other hand, the ligand without amino and methyl substituents (L-4, 1, 4-bis(2-pyridyl)-2,3-diaza-1,3-butadiene) does not induce spontaneous resolution. The resulting compound, [Mn-2(L)(N-3)(4)](n) (4), consists of centrosymmetric 2D layers with alternating single diazine, single EE azido, and double end-on (EO) azido bridges, where the chirality is destroyed by the centrosymmetric double EO bridges. These compounds exhibit very different magnetic behaviors. In particular, 1 behaves as a metamagnet built of homometallic ferrimagnetic chains with a unique "fused-triangles" topology, 2 behaves as a 1 D antiferromagnet with alternating antiferromagnetic interactions, 3a and 3b behave as spin-canted weak ferromagnets with different critical temperatures, and 4 also behaves as a spin-canted weak ferromagnet but exhibits two-step magnetic transitions.
引用
收藏
页码:1419 / 1429
页数:11
相关论文
共 115 条
[41]   Helical coordination polymers from achiral components in crystals. Homochiral crystallization, homochiral helix winding in the solid state, and chirality control by seeding [J].
Ezuhara, T ;
Endo, K ;
Aoyama, Y .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1999, 121 (14) :3279-3283
[42]  
Fu AH, 2002, CHEM-EUR J, V8, P2239, DOI 10.1002/1521-3765(20020517)8:10<2239::AID-CHEM2239>3.0.CO
[43]  
2-7
[44]   Two-dimensional homochiral manganese(II)-azido frameworks incorporating an achiral ligand: Partial spontaneous resolution and weak ferromagnetism [J].
Gao, EQ ;
Bai, SQ ;
Wang, ZM ;
Yan, CH .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2003, 125 (17) :4984-4985
[45]   From manganese(II)-azido layers to a novel three-dimensional molecular magnet: spin canting and metamagnetism [J].
Gao, EQ ;
Wang, ZM ;
Yan, CH .
CHEMICAL COMMUNICATIONS, 2003, (14) :1748-1749
[46]   New one-dimensional azido-bridged manganese(II) coordination polymers exhibiting alternating ferromagnetic-antiferromagnetic interactions: Structural and magnetic studies [J].
Gao, EQ ;
Bai, SQ ;
Yue, YF ;
Wang, ZM ;
Yan, CH .
INORGANIC CHEMISTRY, 2003, 42 (11) :3642-3649
[47]   Molecular tectonics: from enantiomerically pure sugars to enantiomerically pure triple stranded helical coordination network [J].
Grosshans, P ;
Jouaiti, A ;
Bulach, V ;
Planeix, JM ;
Hosseini, MW ;
Nicoud, JF .
CHEMICAL COMMUNICATIONS, 2003, (12) :1336-1337
[48]   The first 3-D ferrimagnetic nickel fumarate with an open framework:: [Ni3(OH)2(O2C-C2H2-CO2)(H2O)4]•2H2O [J].
Guillou, N ;
Pastre, S ;
Livage, C ;
Férey, G .
CHEMICAL COMMUNICATIONS, 2002, (20) :2358-2359
[49]   Synthesis and crystal structure of a triangular nickel(II) complex with the shortest imine-based rigid ligand [J].
Guo, D ;
Duan, CY ;
Fang, CJ ;
Meng, QJ .
JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 2002, (06) :834-836
[50]   Design and crystal structures of triple helicates with crystallographic idealized D3 symmetry:: The role of side chain effect on crystal packing [J].
Guo, D ;
Pang, KL ;
Duan, CY ;
He, C ;
Meng, QJ .
INORGANIC CHEMISTRY, 2002, 41 (23) :5978-5985