Tronic Tristan A, deKrafft Kathryn E, Lim Mi Jung, Ley Amanda N, Pike Robert D
Department of Chemistry, College of William and Mary, Williamsburg, Virginia 23187-8795, USA.
Inorg Chem. 2007 Oct 15;46(21):8897-912. doi: 10.1021/ic7007057. Epub 2007 Sep 13.
Metal-organic networks of CuCN with diimines (L) = pyrazine (Pyz), 2-aminopyrazine (PyzNH(2)), quinoxaline (Qox), phenazine (Phz), 4,4'-bipyridyl (Bpy), pyrimidine (Pym), 2-aminopyrimidine (PymNH(2)), 2,4-diaminopyrimidine (Pym(NH(2))(2)), 2,4,6-triaminopyrimidine (Pym(NH(2))(3)), quinazoline (Qnz), pyridazine (Pdz), and phthalazine (Ptz) were studied. Open reflux reactions produced complexes (CuCN)(2)(L) for L = Qox, Phz, Bpy, PymNH(2), Pym(NH(2))(2), Qnz, and Pdz and (CuCN)(3)(L) complexes for L = Pyz, PyzNH(2), Qox, Bpy, Pym(NH(2))(3), and Pdz. Also produced were (CuCN)(3)(Pyz)(2), (CuCN)(PyzNH(2)), (CuCN)7(Pym)(2), (CuCN)(5)(Qnz)(2) and (CuCN)(5)(Ptz)(2). X-ray structures are presented for (CuCN)(2)(Pdz), (CuCN)(2)(PymNH(2)), and (CuCN)(7)(Pym)(2). Hydrothermal reactions yielded additional X-ray structures of (CuCN)(2)(PyzNH(2)), (CuCN)(3)(Pym(NH(2))(2)), (CuCN)(4)(Qnz), a second (CuCN)(2)(Pdz) phase, (CuCN)(5)(Pdz)2, (CuCN)(2)(Ptz), and (CuCN)(7)(Ptz)2. Structural trends, including cuprophilic interactions and cyano-bridged Cu(2)(CN)(2) dimer formation, are discussed. Particularly short Cu...Cu interactions are noted for the novel 4- and 5-coordinate Cu(2)(CN)(2) dimers. Thermal analyses show that most of the complexes decompose with loss of L around 160-180 degrees C. Luminescence behavior is relatively weak in the products.
对含有二亚胺（L）=吡嗪（Pyz）、2-氨基吡嗪（PyzNH₂）、喹喔啉（Qox）、菲啶（Phz）、4,4'-联吡啶（Bpy）、嘧啶（Pym）、2-氨基嘧啶（PymNH₂）、2,4-二氨基嘧啶（Pym(NH₂)₂）、2,4,6-三氨基嘧啶（Pym(NH₂)₃）、喹唑啉（Qnz）、哒嗪（Pdz）和酞嗪（Ptz）的CuCN金属有机网络进行了研究。开放回流反应生成了配合物（CuCN）₂（L），其中L = Qox、Phz、Bpy、PymNH₂、Pym(NH₂)₂、Qnz和Pdz，以及（CuCN）₃（L）配合物，其中L = Pyz、PyzNH₂、Qox、Bpy、Pym(NH₂)₃和Pdz。还生成了（CuCN）₃（Pyz）₂、（CuCN）（PyzNH₂）、（CuCN）₇（Pym）₂、（CuCN）₅（Qnz）₂和（CuCN）₅（Ptz）₂。给出了（CuCN）₂（Pdz）、（CuCN）₂（PymNH₂）和（CuCN）₇（Pym）₂的X射线结构。水热反应得到了（CuCN）₂（PyzNH₂）、（CuCN）₃（Pym(NH₂)₂）、（CuCN）₄（Qnz）、第二个（CuCN）₂（Pdz）相、（CuCN）₅（Pdz）₂、（CuCN）₂（Ptz）和（CuCN）₇（Ptz）₂的其他X射线结构。讨论了结构趋势，包括亲铜相互作用和氰基桥连的Cu₂(CN)₂二聚体的形成。对于新型的4-和5-配位Cu₂(CN)₂二聚体，注意到了特别短的Cu...Cu相互作用。热分析表明，大多数配合物在160-180℃左右分解并失去L。产物中的发光行为相对较弱。
