摘 要：該課題通過(guò)設(shè)計(jì)結(jié)構(gòu)精確的分子單體，通過(guò)氫鍵、配位作用及疏溶劑作用和pi-pi堆積作用等為驅(qū)動(dòng)力，構(gòu)筑多層次的自組裝體系，進(jìn)而探索組裝體的功能。2013年度，我們根據(jù)計(jì)劃書(shū)要求開(kāi)展工作，在以下幾個(gè)方面取得重要進(jìn)展：（1）設(shè)計(jì)了一類(lèi)三角型平面分子，在其周?chē)雴蜰-苯基聯(lián)二吡啶VB+，通過(guò)葫蘆脲[8]對(duì)兩個(gè)VB單元的強(qiáng)絡(luò)合作用，在水相中實(shí)現(xiàn)了有序蜂窩型超分子有機(jī)框架（SOF）結(jié)構(gòu)的自組裝。（2）設(shè)計(jì)了兩類(lèi)剛性四面體分子，分別引入4個(gè)紫精和四硫富瓦烯片段，在把紫精還原或把四硫富瓦烯氧化為正離子自由基后，這兩類(lèi)正離子自由基在水相強(qiáng)烈堆積，從而誘導(dǎo)其形成三維網(wǎng)絡(luò)超分子組裝結(jié)構(gòu)。（3）利用氫鍵控制芳香酰胺線(xiàn)性分子的構(gòu)象，從而研究其結(jié)構(gòu)-性質(zhì)關(guān)系，并進(jìn)而利用構(gòu)象控制開(kāi)展分子識(shí)別與自組裝研究。①利用單分子力譜首次研究了驅(qū)動(dòng)形成芳香酰胺螺旋孔狀結(jié)構(gòu)的氫鍵的強(qiáng)度及不同位置氫鍵強(qiáng)度的差異；②利用手性離子對(duì)識(shí)別，從并入氫鍵折疊片段的UPy四氫鍵組裝單體構(gòu)筑了一類(lèi)交替堆積的手性超分子聚合物；③設(shè)計(jì)合成了兩個(gè)大環(huán)分子，引入酰胺和1，2，3-三氮唑片段，通過(guò)對(duì)二酰胺和三碘客體分子的氫鍵和鹵鍵結(jié)合，研究了分子間氫鍵和鹵鍵的相對(duì)強(qiáng)度；④設(shè)計(jì)了新的雙卟啉和三卟啉主體分子，通過(guò)分子內(nèi)氫鍵誘導(dǎo)其形成剛性梳型構(gòu)象，進(jìn)而用于研究配位作用和堆積作用協(xié)同誘導(dǎo)的多組分超分子結(jié)構(gòu)組裝。（4）在配位自組裝研究方面取得重要進(jìn)展：①研究了含有氮雜環(huán)卡賓-金屬鍵的金屬有機(jī)大環(huán)分子的合成，發(fā)現(xiàn)氮雜環(huán)卡賓與11族金屬（Cu，Ag，Au）可以形成較強(qiáng)的配位鍵，由此獲得了中間橋連基團(tuán)是不同長(zhǎng)度、含有不同吡啶數(shù)目的系列金屬有機(jī)大環(huán)分子；②對(duì)含有多配位位點(diǎn)的氮雜杯吡啶大環(huán)分子進(jìn)行配位組裝及金屬簇可控合成的機(jī)理進(jìn)行了深入研究。發(fā)現(xiàn)含有多個(gè)配位位點(diǎn)的氮雜杯吡啶大環(huán)分子可以結(jié)合多個(gè)金屬離子，形成一個(gè)分立的組裝結(jié)構(gòu)，并且一種大環(huán)分子與某種特定金屬形成的復(fù)合物結(jié)構(gòu)具有很好的穩(wěn)定性，金屬與配體的比例較為固定。（5）利用柱芳烴為骨架，構(gòu)筑了一類(lèi)新的自組裝單分子納米管，通過(guò)引入由苯丙氨酸構(gòu)成的肽鏈，延長(zhǎng)了單管長(zhǎng)度并引入手性，從而實(shí)現(xiàn)了對(duì)氨基酸跨膜輸送的手性選擇性。

關(guān)鍵詞：自組裝 多層次 氫鍵 配位作用 人工通道

Abstract：We achieved progresses in the following aspects： （1） We designed and synthesized a new kind of triangular planar molecules which were attached with three N-phenyl 4，4’-bipyridyl （BP） units. By utilizing the strong encapsulation of cucurbit[8]uril （CB[8]） for two BP， for the first time， we assembled a series of 2D honeylcomb-styled supramolecular organic framework （SOF）. （2） We designed and prepared two tetrahedral monomers which contained four viologen or tetrathiafulvalene （TTF） units. We found that when the viologen was reduced or TTF was oxidized to its cation radical， due to the tetrahedral feature of the molecules， the cation radicals could strongly dimerize in solution for the molecules to form 3D supramolecular networks. （3） We also succeeded in using hydrogen bonding to control the required conformation of aromatic amide sequences. By investigating their structure-property relationship， we constructed several series of supramolecular systems. ①We utilized single molecular force spectroscopy to evaluate the strength of intramolecular hydrogen bonding； ②By making use of ion pair recognition， we constructed a new kind of alternately arranged chiral supramolecular copolylmers from two aromatic amide-linked UPy ditopic monomers.③We designed and prepared two macrocycles which contained amide and 1，2，3-triazole segments. By investigating their binding toward diamide and triiodide guests， we evaluated the relative strength of intermolecular hydrogen bonding. （4） We also made progresses in the area of coordination self-assembly.①We succeeded in preparing new coordination macrocycles which contained azaheterocyclic carbine units and found that the azaheterocyclic carbenes could coordinate to Cu（II）， Ag （I） or Au （III） to form coordination macrocycles that contained different pyridine rings； ②We also investigated the mechanism of the formation of the above coordination macrocycles and found that the N atoms of pyridines incorporated in the macrocycles might bind to multiple metal ions to form separated entities of high stability. （5） We constructed a new series of single molecular tubes by attaching phenylalanine peptide chains to a pillar[n]arene backbone. In this way， we could extend the length of the pillararene tube and thus insert the tube to lipid bilayers to form a single molecular channel for transporting amino acids that exhibited chiral selectivity.

Key Words： Self-assembly； Multi-level； Hydrogen bond； Coordination； Artificial channel

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