Building Blocks and COFs Formed in Concert -Three-Component Synthesis of Pyrene-Fused Azaacene Covalent Organic Framework in the Bulk and as Films
Building Blocks and COFs Formed in Concert -Three-Component Synthesis of Pyrene-Fused Azaacene Covalent Organic Framework in the Bulk and as Films
复制标题
协同形成的构件和 COF - 芘稠合氮杂苯共价有机框架的本体和薄膜的三组分合成
DOI：
10.1002/anie.202302872
复制
发表时间：
2023
期刊：
影响因子：
--
通讯作者：
Frey L
中科院分区：
文献类型：
--
作者：
Frey L
描述了一种用于形成含有扩展芳族化合物的共价有机框架（COF）的三组分合成方法。值得注意的是，这种方法能够在类似的时间范围内沿着沿着反应景观合成结构单元和COF。使用片段结构单元组分，即作为聚集诱导COF前体的芘二酮二硼酸和作为延伸官能化单元的二氨基间苯二胺（Ph）、2，3-二氨基萘（Naph）或（1 R，2 R）-（+）-1，2-二苯基乙二胺（2 Ph）连同2，3，6，7，10，11-六羟基苯并菲，导致形成相应的芘稠合氮杂并苯，即，Aza-COF系列具有二酮部分的完全转化、长程有序和高表面积。此外，新的三组分合成成功地应用于在各种基底上制备具有纳米结构表面的Aza-COF的高度结晶的取向薄膜。Aza-COF在蓝色光谱区域表现出光吸收最大值，并且每个Aza-COF呈现出不同的光致发光曲线。Aza‐Ph‐和Aza‐Naph‐COFs的瞬态吸收测量表明这些COFs内激发态的超快弛豫动力学。
A three‐component synthesis methodology is described for the formation of covalent organic frameworks (COFs) containing extended aromatics. Notably, this approach enables synthesis of the building blocks and COF along parallel reaction landscapes, on a similar timeframe. The use of fragmental building block components, namely pyrene dione diboronic acid as aggregation‐inducing COF precursor and the diamineso‐phenylenediamine (Ph), 2,3‐diaminonaphthalene (Naph), or (1R,2R)‐(+)‐1,2‐diphenylethylenediamine (2Ph) as extending functionalization units in conjunction with 2,3,6,7,10,11‐hexahydroxytriphenylene, resulted in the formation of the corresponding pyrene‐fused azaacene, i.e., Aza‐COF series with full conversion of the dione moiety, long‐range order, and high surface area. In addition, the novel three‐component synthesis was successfully applied to produce highly crystalline, oriented thin films of the Aza‐COFs with nanostructured surfaces on various substrates. The Aza‐COFs exhibit light absorption maxima in the blue spectral region, and each Aza‐COF presents a distinct photoluminescence profile. Transient absorption measurements of Aza‐Ph‐ and Aza‐Naph‐COFs suggest ultrafast relaxation dynamics of excited‐states within these COFs.