Supramolecular Organic Frameworks of Brominated Bisphenol Derivatives with Organoamines

Reactions of two brominated bisphenol derivatives, tetrabromobisphenol-F (TBBPF) and tetrabromobisphenol-A (TBBPA), with various organoamines resulted in six supramolecular organic frameworks (SOFs), formulated as (TBBPF2–)2·(HPZ+)2·(H2PZ2+) (1), (TBBPF–)2·(H2PZ2+)·2H2O·2MeOH (2), (TBBPF)·(TBBPF–)·(HDABCO+)·H2O (3), (TBBPF)·(HMTA) (4), (TBBPA)·(HMTA) (5), and (TBBPA)3·(HMTA)3·H2O (6) (PZ = piperazine; DABCO = diazabicyclo[2.2.2]octane; HMTA = hexamethylenetetramine). Compounds 1–6 were characterized by single-crystal and powder X-ray diffractions. The predominant driving forces in 1–6 are hydrogen bonds (H-bonds), by which the compounds assemble into supramolecular organic frameworks with versatile topological structures. Compound 1 contains TBBPF/PZ in a 2:3 ratio and exhibits 2D (two-dimensional) H-bonded supramolecular 44-sql layer structure built by the four-connected {H2PZ2+} moieties and {TBBPF2–}. Compound 2 shows a 2-fold interpenetrated 3D (three-dimensional) H-bonded networks comprised by TBBPF/PZ in 2:1 ratio with the presence of solvent H2O and MeOH molecules, in which two identical pcu topological nets are recognized by choosing a decamer synthons as nodes. Compound 3 displays H-bonded 44-sql layer structure built by 2:1 TBBPF and DABCO, as well as one H2O per formula unit. Compounds 4 and 5 assemble into 1D (one-dimensional) H-bonded zigzag chains via the alternate linkage of HMTA with TBBPF/TBBPA in a similar fashion. Compound 6 generates an interesting hexamer subunit (HMTA···TBBPA···HMTA···TBBPA···HMTA···TBBPA), which can be viewed as a fragment of three repeating units for a zigzag chain observed in compound 5. A pair of the hexamer subunits is further connected by two water molecules to form an H-bonded molecular oligomer. Importantly, halogen bonds (X-bonds) have been observed in compounds 4–6 that exhibit 1D and 0D H-bonded supramolecular structures.

两种溴化双酚衍生物，四溴双酚-F（TBBPF）和四溴双酚-A（TBBPA）与多种有机胺反应，生成了六种超分子有机框架（SOFs），其化学式分别为：(TBBPF2–)2·(HPZ+)2·(H2PZ2+)（1），(TBBPF–)2·(H2PZ2+)·2H2O·2MeOH（2），(TBBPF)·(TBBPF–)·(HDABCO+)·H2O（3），(TBBPF)·(HMTA)（4），(TBBPA)·(HMTA)（5），以及(TBBPA)3·(HMTA)3·H2O（6）（PZ为哌嗪；DABCO为1,4-二氮杂环辛烷；HMTA为六甲基乙烯四胺）。化合物1–6通过单晶和粉末X射线衍射进行了表征。在这些化合物中，主要的驱动力为氢键（H-bonds），通过这些氢键，化合物组装成具有多样拓扑结构的超分子有机框架。化合物1中TBBPF/PZ的比例为2:3，并呈现出由四个相连的{H2PZ2+}单元和{TBBPF2–}单元构建的二维（two-dimensional）氢键结合的超分子44-sql层结构。化合物2展示了一种由TBBPF/PZ（比例为2:1）组成的双交叉三维（three-dimensional）氢键网络，其中包含溶剂H2O和MeOH分子，通过选择十元合成为节点，识别出两个相同的pcu拓扑网络。化合物3展现出由2:1比例的TBBPF和DABCO构建的氢键结合的44-sql层结构，每个分子单元中含有一个H2O分子。化合物4和5通过HMTA与TBBPF/TBBPA的交替连接，组装成一维（one-dimensional）氢键的之字形链。化合物6生成一个有趣的六元亚基（HMTA···TBBPA···HMTA···TBBPA···HMTA···TBBPA），这可以视为在化合物5中观察到的之字形链三个重复单元的片段。一对六元亚基通过两个水分子进一步连接，形成一个氢键结合的分子寡聚物。值得注意的是，在展现出1D和0D氢键结合超分子结构的化合物4–6中，观察到了卤键（X-bonds）。