Syntheses, structural analyses, and magneto-structural correlations of three polymeric Fe(II) complexes with azide ligand.
Syntheses, structural analyses, and magneto-structural correlations of three polymeric Fe(II) complexes with azide ligand.
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DOI：
10.1021/ic034423o
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发表时间：
2003-08
影响因子：
4.6
通讯作者：
Sanjit Konar;E. Zangrando;M. Drew;T. Mallah;J. Ribas;N. R. Chaudhuri
中科院分区：
文献类型：
--
作者：
Sanjit Konar;E. Zangrando;M. Drew;T. Mallah;J. Ribas;N. R. Chaudhuri
三种新的金属有机聚合物配合物[Fe（N（3））（2）（bpp）（2）]（1），[Fe（N（3））（2）（bpe）]（2），[Fe（N（3））（2）（phen）]（3）[bpp =（1，3-双（4-吡啶基）-丙烷），bpe =合成了1，2-二（4-吡啶基）乙烷，phen = 1，10-菲咯啉]，并在300- 2K范围内进行了单晶X射线衍射和低温磁性测量。配合物1和2在单斜晶系中结晶，空间群C2/c，具有以下晶胞参数：a = 19.355（4）A，B = 7.076（2）A，c = 22.549（4）A，β = 119.50（3）度，Z = 4，a = 10.007（14）A，B = 13.789（18）A，c = 10.377（14）A，β = 103.50（1）度，Z = 4。配合物3在三斜晶系中结晶，空间群P（-）1，其中a = 7.155（12）A，B = 10.066（14）A，c = 10.508（14）A，α = 109.57（1）度，β = 104.57（1）度，γ = 105.10（1）度，并且Z = 2。所有配位聚合物都具有八面体Fe（II）节点。1的结构测定揭示了（4，4）拓扑结构的2D层的平行互穿结构，其由通过bpp配体连接的Fe（II）节点形成，而单配位的叠氮阴离子从波纹片悬垂。配合物2具有通过bpe配体互连的1D双端对端叠氮桥接铁（II）链构建的2D排列。配合物3显示了聚合物排列，其中金属离子通过成对的端对和端对端叠氮化物配体互连，表现出金属的锯齿形排列（Fe-Fe-Fe角为111.18度）和3.347 A（通过EO叠氮化物）和5.229 A（EE叠氮化物）的金属间分离。变温磁化率数据表明，在1中的金属中心之间没有磁相互作用，而在2中，通过端到端叠氮化物桥存在反铁磁相互作用。配合物3显示铁以及反铁磁的金属中心之间的相互作用，通过交替的端对端和端到端的叠氮桥。配合物1已被建模使用D参数（考虑扭曲的八面体Fe（II）的几何形状和任何可能的J值等于零）和配合物2已被建模为一维系统与经典和/或量子自旋，我们已经使用了两种可能的全对角化过程：没有和与D参数，考虑到重要的扭曲的Fe（II）离子。对于复合体3，交替耦合模型阻碍了经典自旋建模的数学解决方案。在量子自旋的情况下，建模已经如在2中那样进行。
Three new metal-organic polymeric complexes, [Fe(N(3))(2)(bpp)(2)] (1), [Fe(N(3))(2)(bpe)] (2), and [Fe(N(3))(2)(phen)] (3) [bpp = (1,3-bis(4-pyridyl)-propane), bpe = (1,2-bis(4-pyridyl)-ethane), phen = 1,10-phenanthroline], have been synthesized and characterized by single-crystal X-ray diffraction studies and low-temperature magnetic measurements in the range 300-2 K. Complexes 1 and 2 crystallize in the monoclinic system, space group C2/c, with the following cell parameters: a = 19.355(4) A, b = 7.076(2) A, c = 22.549(4) A, beta = 119.50(3) degrees, Z = 4, and a = 10.007(14) A, b = 13.789(18) A, c = 10.377(14) A, beta = 103.50(1) degrees, Z = 4, respectively. Complex 3 crystallizes in the triclinic system, space group P(-)1, with a = 7.155(12) A, b = 10.066(14) A, c = 10.508(14) A, alpha = 109.57(1) degrees, beta = 104.57(1) degrees, gamma = 105.10(1) degrees, and Z = 2. All coordination polymers exhibit octahedral Fe(II) nodes. The structural determination of 1 reveals a parallel interpenetrated structure of 2D layers of (4,4) topology, formed by Fe(II) nodes linked through bpp ligands, while mono-coordinated azide anions are pendant from the corrugated sheet. Complex 2 has a 2D arrangement constructed through 1D double end-to-end azide bridged iron(II) chains interconnected through bpe ligands. Complex 3 shows a polymeric arrangement where the metal ions are interlinked through pairs of end-on and end-to-end azide ligands exhibiting a zigzag arrangement of metals (Fe-Fe-Fe angle of 111.18 degrees) and an intermetallic separation of 3.347 A (through the EO azide) and of 5.229 A (EE azide). Variable-temperature magnetic susceptibility data suggest that there is no magnetic interaction between the metal centers in 1, whereas in 2 there is an antiferromagnetic interaction through the end-to-end azide bridge. Complex 3 shows ferro- as well as anti-ferromagnetic interactions between the metal centers generated through the alternating end-on and end-to-end azide bridges. Complex 1 has been modeled using the D parameter (considering distorted octahedral Fe(II) geometry and with any possible J value equal to zero) and complex 2 has been modeled as a one-dimensional system with classical and/or quantum spin where we have used two possible full diagonalization processes: without and with the D parameter, considering the important distortions of the Fe(II) ions. For complex 3, the alternating coupling model impedes a mathematical solution for the modeling as classical spins. With quantum spin, the modeling has been made as in 2.