Department of Chemistry, Simon Fraser University, 8888 University Drive, Burnaby, BC, Canada V5A 1S6.
J Am Chem Soc. 2009 Dec 30;131(51):18435-44. doi: 10.1021/ja907519c.
Four new coordination polymers, Mn(Clterpy)Au(CN)(2) (Clterpy = 4'-chloro-2,2';6',2''-terpyridine), Mn(Brterpy)Au(CN)(2) (Brterpy = 4'-bromo-2,2';6',2''-terpyridine), Pb(Clterpy)Au(CN)(2), and Pb(Brterpy)(mu-OH(2))(0.5)Au(CN)(2) were synthesized and structurally characterized, and their birefringence values were measured. The supramolecular structures of the two Mn(II) polymers are the same: they form one-dimensional (1D) chains of Mn(Xterpy)Au(CN)(2) units (X = Cl, Br), each having one bridging and one terminal Au(CN)(2)(-). The Pb(II) analogues form 1D polymers containing chains of Pb(Xterpy)Au(CN)(2) linked via Au(CN)(2)(-) units. Pb(Brterpy)(mu-OH(2))(0.5)Au(CN)(2) also contains a bridging water unit. In the plane of the primary crystal growth direction, the birefringence values of the four coordination polymers were found to be 0.378(19), 0.50(3), 0.38(2), and 0.26(3), respectively. The birefringence values are related to the supramolecular structures in terms of maximizing the alignment of the terpyridine-based units and the maximum off-axis positioning of the C-X bonds. With the exception of that for the Pb(Brterpy)(mu-OH(2))(0.5)Au(CN)(2) polymer, the birefringence values are either as large as or significantly larger than in the related M(2,2';6',2''-terpyridine)Au(CN)(2) systems. These polymers illustrate the utility of adding polarizable carbon-halogen bonds as a design element in highly birefringent coordination polymers.
四种新的配位聚合物，Mn(Clterpy)Au(CN)(2) (Clterpy = 4'-氯-2,2';6',2''-三联吡啶），Mn(Brterpy)Au(CN)(2) (Brterpy = 4'-溴-2,2';6',2''-三联吡啶），Pb(Clterpy)Au(CN)(2)和 Pb(Brterpy)(mu-OH(2))(0.5)Au(CN)(2)被合成并进行了结构表征，同时测量了它们的双折射值。两种 Mn(II)聚合物的超分子结构相同：它们形成一维（1D）的 Mn(Xterpy)Au(CN)(2)单元（X = Cl, Br）链，每个单元都有一个桥连和一个末端的 Au(CN)(2)(-)。Pb(II)类似物形成 1D 聚合物，其中包含通过 Au(CN)(2)(-)单元连接的 Pb(Xterpy)Au(CN)(2)链。Pb(Brterpy)(mu-OH(2))(0.5)Au(CN)(2)还包含一个桥连水单元。在主要晶体生长方向的平面内，四种配位聚合物的双折射值分别为 0.378(19)、0.50(3)、0.38(2)和 0.26(3)。双折射值与超分子结构有关，通过最大限度地使三联吡啶基单元对齐和使 C-X 键最大程度地偏离轴来实现。除了 Pb(Brterpy)(mu-OH(2))(0.5)Au(CN)(2)聚合物外，其余聚合物的双折射值要么与相关的 M(2,2';6',2''-三联吡啶）Au(CN)(2)系统一样大，要么显著大于该系统。这些聚合物说明了在高双折射配位聚合物中添加可极化的碳卤键作为设计元素的效用。
