Braml Nicole E, Stegbauer Linus, Lotsch Bettina V, Schnick Wolfgang
Department Chemie, University of Munich (LMU), Butenandtstrasse 5-13, 81377 München (Germany), Fax: (+49) 89-2180-77440.
Chemistry. 2015 May 18;21(21):7866-73. doi: 10.1002/chem.201405023. Epub 2015 Apr 23.
In this contribution, we report on novel functionalized triazines, which represent new precursors for C/N/(H) compounds or suitable building blocks for carbon-based functional networks. Our results provide insights into the structural properties of molecular carbon nitride materials and their design principles. Tris(1-propynyl)-1,3,5-triazine (C3 N3 (C3 H3 )3 ) and tris(1-butynyl)-1,3,5-triazine (C3 N3 (C4 H5 )3 ) were prepared by substitution reactions of cyanuric chloride (C3 N3 Cl3 ) with prop-1-yne and but-1-yne. The crystal structure of tris(1-propynyl)-1,3,5-triazine was solved in the orthorhombic space group Pbcn (Z=4, a=1500.06 (14), b=991.48(10), c=754.42(6) pm, V=1122.03(18)×10(6) pm(3) ), whereas tris(1-butynyl)-1,3,5-triazine crystallized in the triclinic space group P-1 (Z=6, a=1068.36(12), b=1208.68(12), c=1599.38(16) pm, α=86.67(3), β=86.890(4), γ=86.890(4)°, V=1997.7(4)×10(6) pm(3) ). For both structures, planar triazine units and layerlike packing of the molecules were observed. Tris(1-propynyl)-1,3,5-triazine is built up from hydrogen-bonded zig-zag strands, whereas tris(1-butynyl)-1,3,5-triazine shows parallel layered arrangements. Both compounds were investigated by NMR spectroscopy, IR spectroscopy, and differential thermal analysis/thermogravimetric analysis, which provided insights into their structural, chemical, and thermal properties. In addition, tris(1-propynyl)-1,3,5-triazine was pyrolyzed and a new polymeric triazine-based compound containing mesitylene units was obtained. Its structural features and properties are discussed in detail.
在本论文中，我们报道了新型功能化三嗪，它们是C/N/(H)化合物的新前体或碳基功能网络的合适构建单元。我们的结果为分子氮化碳材料的结构性质及其设计原理提供了见解。三（1-丙炔基）-1,3,5-三嗪（C3N3(C3H3)3）和三（1-丁炔基）-1,3,5-三嗪（C3N3(C4H5)3）通过氰尿酰氯（C3N3Cl3）与丙-1-炔和丁-1-炔的取代反应制备。三（1-丙炔基）-1,3,5-三嗪的晶体结构在正交空间群Pbcn中解析（Z = 4，a = 1500.06(14)，b = 991.48(10)，c = 754.42(6) pm，V = 1122.03(18)×10(6) pm(3)），而三（1-丁炔基）-1,3,5-三嗪结晶于三斜空间群P-1（Z = 6，a = 1068.36(12)，b = 1208.68(12)，c = 1599.38(16) pm，α = 86.67(3)，β = 86.890(4)，γ = 86.890(4)°，V = 1997.7(4)×10(6) pm(3)）。对于这两种结构，均观察到平面三嗪单元和分子的层状堆积。三（1-丙炔基）-1,3,5-三嗪由氢键连接的之字形链构成，而三（1-丁炔基）-1,3,5-三嗪呈现平行的层状排列。通过核磁共振光谱、红外光谱以及差示热分析/热重分析对这两种化合物进行了研究，这些分析为它们的结构、化学和热性质提供了见解。此外，对三（1-丙炔基）-1,3,5-三嗪进行热解，得到了一种含均三甲苯单元的新型基于三嗪的聚合物化合物。详细讨论了其结构特征和性质。
