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Pushing Synthesis toward the Maximum Generation Range of Dendritic Macromolecules
Macromolecules ( IF 5.5 ) Pub Date : 2018-07-13 00:00:00 , DOI: 10.1021/acs.macromol.8b00891
Daniel Messmer , Martin Kröger , A. Dieter Schlüter

The maximum generation gmax of a dendritic molecule denotes the value of the generation number g, above which such a compound cannot be synthesized without defects anymore due to steric constraints. For dendronized polymers (DPs), such a densely packed regime is entered far earlier (gmax ≈ 6) than it is for comparable dendrimers (gmax ≥ 10) because dendritic side chains are confined to a cylindrical rather than a spherical volume. We here report a long sought-after improvement to a key step in the divergent synthesis of high-g DPs which enabled obtaining the polymers of g = 6, 7, and 8. These DPs are of unprecedented dendritic perfection, and the representatives with g > 6 are to our knowledge the first molecules for which gmax has been surpassed. We suggest a straightforward parameter α which allows to assess whether any dendritic molecule is above gmax, given sufficiently efficient chemistry and the possibility of accurately determining the number of defects. Finally, we correlate gel permeation chromatography results and atomic force microscopic images with defect rates.

中文翻译:

将合成推向树枝状大分子的最大生成范围

树状分子的最大生成量g max表示生成数g的值,在该值以上,由于空间限制,不能再无缺陷地合成这样的化合物。对于树枝状聚合物(DPS),进入这样的密集堆积政权远远早(最大≈6)比它可比树枝状聚合物(最大值≥10)因为树突侧链被限制于圆柱形,而不是一个球形体积。我们在这里报告了长期寻求的改进方法,该改进方法是高g DP的不同合成中的关键步骤的关键步骤,从而能够获得g的聚合物= 6、7和8。这些DP具有前所未有的树突状完美性,据我们所知,g > 6的代表是第一个超过g max的分子。我们建议一个简单的参数α ,如果化学足够有效并且可以准确确定缺陷数量,则可以评估树突状分子是否高于g max。最后,我们将凝胶渗透色谱结果和原子力显微镜图像与缺陷率相关联。
更新日期:2018-07-13
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