Multigram synthesis of an octaaminocryptand L (1,4,11,14,17,27,29,36-octaazapentacyclo[12.12.12.2.^6,92.^19,222^31,34]tetratetraconta-6(43),7,9(44),19(41),20,22(42),31(39),32,34(40)-nonane, N(CH₂CH₂NHCH₂-p-xylyl-CH₂NHCH₂CH₂)₃N) with high yield was obtained in one pot by low temperature [2 + 3] condensation of tris(2-aminoethyl)amine with terephthalaldehyde followed by sodium borohydride reduction in methanol. L was treated with hydrochloric, hydroiodic, and picric acids in different experimental conditions to obtain crystals of different salts of L having different degrees of protonation. Structural aspects of binding of halides, picrate, and water in protonated L were examined thoroughly. Crystallographic results show that a diprotonated chloride complex of L, [H₂L](Cl)₂·3H₂O (1) and (triprotonated and monoprotonated) species of L in an iodide complex [{H₃L}{HL}](I)₄ (2) do not show any guest encapsulation inside the cavity, whereas one molecule of water resides inside the cavity in the case of its triprotonated state where one of the bridgehead nitrogen atoms is protonated in [2{LH₃(H₂O)}](I)₆·2H₂O (3). Importantly, in a tertraprotonated picrate complex of L, [H₄L(H₂O)_2.50](picrate)₄·2CH₃CN, 5, two water molecules reside inside the two N4 cavities of L, bridged by a third water molecule showing tritopic binding, whereas in the octaprotonated state a monotopic encapsulation of iodide via N−H···iodide and C−H···iodide interactions was observed inside the receptor cavity of [H₈L(I)](I)₇·9H₂O, (8). This study systematically represents a competition between anion and solvent recognition upon different degrees of protonation of L. Further detailed structural analysis on complex 1 shows the formation of a one-dimensional polymeric water chloride hybrid network of linear rectangular chains sandwiched between the cryptand layers.

中文翻译：

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不同质子化程度的八氨基隐烯分子的分子识别研究

一个octaaminocryptand的多克合成大号（1,4,11,14,17,27,29,36-octaazapentacyclo [12.12.12.2。^6,9- 2. ^19,22 2 ^31,34 ] tetratetraconta-6（43），7 ，9（44），19（41），20,22（42），31（39），32,34（40） -壬烷，N（CH ₂ CH ₂ NHCH ₂ - p -二甲苯基CH ₂ NHCH ₂ CH ₂）通过三[2-氨基乙基]胺与对苯二甲醛的低温[2 + 3]缩合，然后在甲醇中将硼氢化钠还原，在一个锅中以高收率获得₃ N）。大号用盐酸，氢碘酸和苦味酸在不同的实验条件下处理，得到质子化程度不同的L盐的不同晶体。彻底检查了质子化L中卤化物，苦味酸盐和水结合的结构方面。晶体学结果表明，碘化物络合物中的L，[H ₂ L ]（Cl）₂ ·3H ₂ O（1）和L的（三质子化和单质子化）双质子化的氯化物络合物[{H ₃ L } {H L } ] [I）₄（2）不会在腔体内显示任何客体封装，而在其三重质子化状态下，桥头氮原子之一被质子化为[2 {L H ₃（H ₂ O）}]时，一分子水会留在腔体内（I）₆ ·2H ₂ O（3）。重要的是，在L的_四质子化苦味酸盐复合物中，[H ₄ L（H ₂ O）_2.50 ]（苦味酸盐）₄ ·2CH ₃ CN，5中，两个水分子位于L的两个N4腔内，由显示三位结合的第三个水分子桥接，而在八质子化状态下，在[H ₈ L（ I）]（I）₇ ·9H ₂ O，（8）。这项研究系统地代表了L质子化程度不同时阴离子和溶剂识别之间的竞争。对复合物1的进一步详细结构分析表明，形成了夹在穴状分子层之间的线性矩形链的一维聚合物水氯化物杂化网络。