Synthesis of triazine-based materials by functionalization with alkynes.
Synthesis of triazine-based materials by functionalization with alkynes.
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DOI：
10.1002/chem.201405023
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发表时间：
2015-05
期刊：
影响因子：
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通讯作者：
Nicole E. Braml;Linus Stegbauer;B. Lotsch;W. Schnick
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文献类型：
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作者：
Nicole E. Braml;Linus Stegbauer;B. Lotsch;W. Schnick
在这篇文章中，我们报道了新型官能化的三嗪类化合物，它们代表了C/N/(H)化合物的新前体或碳基功能网络的合适构建块。我们的结果为分子碳氮化物材料的结构性质及其设计原则提供了深入的见解。以三聚氰酸氯(C3N3CL3)为原料，与丙炔和丁炔反应，合成了三(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)。三(1-丙炔基)-1，3，5-三嗪的晶体结构为Pbcn(Z=4，a=1500.06(14)，b=991.48(10)，c=754.42(6)Pm，V=1122.03(18)×10(6)Pm(3))，三(1-丁炔基)-1，3，5-三嗪为三斜晶空间群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=1997.7(4)×10(6)PM(3)，V=86.890(4)°。对于这两种结构，都观察到了平面的三嗪单元和分子的层状堆积。三(1-丙炔基)-1，3，5-三嗪由氢键形成的锯齿状链构筑而成，而三(1-丁炔基)-1，3，5-三嗪呈平行层状排列。通过核磁共振光谱、红外光谱和差热分析/热重分析对这两种化合物进行了表征，揭示了它们的结构、化学性质和热学性质。此外，还对三(1-丙炔基)-1，3，5-三嗪进行了裂解反应，得到了一种新的含均三甲苯基团的聚合物。详细讨论了它的结构特点和性能。
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.