Noria and its derivatives as hosts for chemically and thermally robust Type II porous liquids.
Noria and its derivatives as hosts for chemically and thermally robust Type II porous liquids.
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Noria及其衍生物作为化学和热稳健II型多孔液体的宿主。
DOI：
10.1039/d1sc03367k
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发表时间：
2021-11-03
期刊：
影响因子：
8.4
通讯作者：
James SL
中科院分区：
文献类型：
--
作者：
Alexander FM;Fonrouge SF;Borioni JL;Del Pópolo MG;Horton PN;Coles SJ;Hutchings BP;Crawford DE;James SL
多孔液体（PL）是一类兼具流动性和永久孔隙性的新型材料。因此，它们可以充当增强的选择性溶剂，并最终可能找到多孔固体无法实现的应用，例如连续流动分离过程。 II 型 PL 由溶解在尺寸排除溶剂中的空分子主体组成，迄今为止主要基于化学和热稳定性有限的主体。在这里，我们确定了 Noria，一种刚性环状低聚物，作为合成更稳健的 II 型 PL 的新宿主。尽管 Noria 的结构已有详细记录，但我们发现文献忽略了 Noria 样品的真实成分。我们发现，批量样品通常由 Noria（约 40%）、Noria 异构体，特别是间苯二酚三聚体“R3”（约 30%）和其他未鉴定的低聚物（约 30%）组成。 Noria 已被结晶学表征为二乙醚溶剂化物，并且首次完全指定了其 1H NMR 谱。先前假设但未报道的 R3 也已在晶体学上被表征为二甲亚砜溶剂化物，这证实了其与 Noria 的替代连接性。 Noria 和 R3 的溶解度较低，这妨碍了它们在 II 型 PL 中的使用，然而，部分乙基化衍生物 Noria-OEt 溶解在尺寸排除溶剂 15-crown-5 中，得到新的 II 型 PL。该 PL 表现出对甲烷 (CH4) 气体的吸收增强，支持液体中存在空孔。详细的分子动力学模拟支持液体中存在孔隙，并表明 CH4 有利于占据孔隙。总体而言，这项工作修改了普遍接受的 Noria 样品的组成，并表明 Noria 衍生物适合合成更稳健的 II 型 PL。多孔液体（PL）是一类兼具流动性和永久孔隙性的新型材料。在这里，我们确定了 Noria，一种刚性环状低聚物，作为合成更稳健的 II 型 PL 的新宿主。
Porous Liquids (PLs) are a new class of material that possess both fluidity and permanent porosity. As such they can act as enhanced, selective solvents and may ultimately find applications which are not possible for porous solids, such as continuous flow separation processes. Type II PLs consist of empty molecular hosts dissolved in size-excluded solvents and to date have mainly been based on hosts that have limited chemical and thermal stability. Here we identify Noria, a rigid cyclic oligomer as a new host for the synthesis of more robust Type II PLs. Although the structure of Noria is well-documented, we find that literature has overlooked the true composition of bulk Noria samples. We find that bulk samples typically consist of Noria (ca. 40%), a Noria isomer, specifically a resorcinarene trimer, “R3” (ca. 30%) and other unidentified oligomers (ca. 30%). Noria has been characterised crystallographically as a diethyl ether solvate and its 1H NMR spectrum fully assigned for the first time. The previously postulated but unreported R3 has also been characterised crystallographically as a dimethyl sulfoxide solvate, which confirms its alternative connectivity to Noria. Noria and R3 have low solubility which precludes their use in Type II PLs, however, the partially ethylated derivative Noria-OEt dissolves in the size-excluded solvent 15-crown-5 to give a new Type II PL. This PL exhibits enhanced uptake of methane (CH4) gas supporting the presence of empty pores in the liquid. Detailed molecular dynamics simulations support the existence of pores in the liquid and show that occupation of the pores by CH4 is favoured. Overall, this work revises the general accepted composition of bulk Noria samples and shows that Noria derivatives are appropriate for the synthesis of more robust Type II PLs. Porous Liquids (PLs) are a new class of material that possess both fluidity and permanent porosity. Here we identify Noria, a rigid cyclic oligomer as a new host for the synthesis of more robust Type II PLs.
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