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首页> 外文期刊>Crystal growth & design >Dual Behavior of Bromine Atoms in Supramolecular Chemistry: The Crystal Structure and Magnetic Properties of Two Copper(II) Coordination Polymers
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Dual Behavior of Bromine Atoms in Supramolecular Chemistry: The Crystal Structure and Magnetic Properties of Two Copper(II) Coordination Polymers

机译：超分子化学中溴原子的双重行为：两种铜（II）配位聚合物的晶体结构和磁性

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The crystal structures of two copper(II) chloride coordination polymers, (Cu-2(2bp)(2)Cl-4)n, henceforth polydimer, and (Cu-3(2bp)(2)Cl-6)n, henceforth polytrimer, where 2bp = 2-bromopyridine, and the temperature dependence of their magnetic susceptibilities are reported. Also, the temperature dependence of the magnetic susceptibility of the monomeric complex, Cu(2bp)(2)Cl-2, is reported. The magnetic data were measured in the range 2-310 K. The organic bromine atom of the 2bp ligand shows electrophilic and nucleophilic character: an electrophilic nature via C-Br...Cl interactions and a nucleophilic nature via Cu...(pi)Br interactions. The Cu...(p)Br interactions, previously underestimated in the literature, turn the 2bp ligand to a bidentate rather than monodentate ligand via the N-Cu coordination bond and the Cu...(pi)Br noncovalent interactions. Thus, the 2bp ligand behaves as a molecular bender; the Cu...(pi)Br interactions result in the bending of the (CuCl2)n infinite linear extended chains at specific locations. The magnetic data of the monomer were fit to the two-dimensional S = 1/2 Heisenberg model (Curie constant = 0.43(1) emu-K/mol-Oe and an exchange constant J/k = 0.41(4) K). The magnetic data of the polydimer were best fit to an alternating antiferromagnetic chain rather than a dimer model (Curie constant = 0.415(3), J(1)/k = -11.4(1) K, J(2)/k = -2.2(3) K). The magnetic data of the polytrimer may be approximated by a model including both nearest neighbor (J(1)) and next nearest neighbor (J(2)) interactions within the polytrimer as well as a Curie-Weiss correction for intertrimer exchange within a single chain [J(1) = -53(1) K, J(2) = -6.0(5) K, theta = -1.5(5) K]. Viewing the reported structures as bent coordination polymers is supported by observations that (a) the Cu...Cl coordination distance is quite short (avg. = 2.672 angstrom) and (b) the magnetic data of the polydimer are best fit to the alternating antiferromagnetic chain model.
机译：两种铜（II）氯化铜配位聚合物（Cu-2（2bp）（2）Cl-4）n（此后为聚二聚体）和（Cu-3（2bp）（2）Cl-6）n的晶体结构报道了其中2bp ＝ 2-溴吡啶的聚三聚体，及其磁化率的温度依赖性。另外，还报告了单体配合物Cu（2bp）（2）Cl-2的磁化率与温度的关系。在2-310 K范围内测量了磁性数据。2bp配体的有机溴原子显示出亲电和亲核特性：通过C-Br ... Cl相互作用形成亲电特性，并通过Cu ...（pi溴相互作用。先前在文献中被低估的Cu ...（p）Br相互作用会通过N-Cu配位键和Cu ...（pi）Br非共价相互作用将2bp配体转变为二齿而不是单齿配体。因此，2bp配体起分子弯曲剂的作用。 Cu ...（pi）Br相互作用导致（CuCl2）n无限线性延伸链在特定位置弯曲。单体的磁性数据拟合到二维S = 1/2 Heisenberg模型（居里常数= 0.43（1）emu-K / mol-Oe和交换常数J / k = 0.41（4）K）。聚二聚体的磁数据最适合于交替的反铁磁链而不是二聚体模型（居里常数= 0.415（3），J（1）/ k = -11.4（1）K，J（2）/ k =- 2.2（3）K）。可以通过一个模型来估算聚三聚体的磁数据，该模型包括聚三聚体中的最近邻（J（1））和下一个最近邻（J（2））相互作用，以及用于单个单体间三聚体交换的居里-魏斯校正链[J（1）= -53（1）K，J（2）= -6.0（5）K，θ= -1.5（5）K]。观察到的以下观点支持将报告的结构视为弯曲配位聚合物：（a）Cu ... Cl配位距离非常短（平均= 2.672埃），并且（b）聚二聚体的磁数据最适合交变反铁磁链模型。

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