基于单吡咯并四硫富瓦烯的稳定电荷转移盐凝胶的构筑
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摘要
设计合成了一种含有冠醚和L-谷氨酰胺基团的单吡咯并四硫富瓦烯三元低分子量凝胶因子.实验表明,本体凝胶在引入无机氧化剂的情况下可以转变为稳定的电荷转移盐凝胶.进一步研究表明,分子间氢键、π-π堆积、S…S相互作用和电荷转移相互作用是形成有机凝胶的主要驱动力.凝胶在外界刺激作用下呈现可逆的宏观相态变化,电荷转移盐凝胶可以可逆转化为原始的凝胶体系;在四氢呋喃中形成的本体凝胶对水非常敏感,少量水的加入即可导致凝胶迅速坍塌.该研究为构筑功能性软材料提供了新的研究思路.
A novel triad gelator based on monopyrrolotetrathiafulvalene containing crown ether and L-glutamine groups have been designed and synthesized.The native gel could be transformed into the charge transfer(CT) salt gels with inorganic oxidants.Further studies revealed that intermolecular hydrogen-bonding,π-π stacking,S…S interaction as well as CT interaction are the main driving forces for the formation of the organogels.The gel shows a reversible macroscopic volume phase transition responding to temperature and ultrasound,as well as the CT salt gels could be reversible transformed to original gel systems.Intriguingly,the native gel form in THF is quite sensitive to water,and addition of small amount of water induce rapid gel collapse.This study lays a new thought for constructing some functional soft materials.
A novel triad gelator based on monopyrrolotetrathiafulvalene containing crown ether and L-glutamine groups have been designed and synthesized.The native gel could be transformed into the charge transfer(CT) salt gels with inorganic oxidants.Further studies revealed that intermolecular hydrogen-bonding,π-π stacking,S…S interaction as well as CT interaction are the main driving forces for the formation of the organogels.The gel shows a reversible macroscopic volume phase transition responding to temperature and ultrasound,as well as the CT salt gels could be reversible transformed to original gel systems.Intriguingly,the native gel form in THF is quite sensitive to water,and addition of small amount of water induce rapid gel collapse.This study lays a new thought for constructing some functional soft materials.
引文
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[3] KISHIMURA A,YAMASHITA T,YAMAGUCHI K,et al.Rewritable phosphorescent paper by the control of competing kinetic and thermodynamic self-assembling events[J].Nature Materials,2005,4(6):546.
[4] YU Z Y,ZHANG J,COULSTON R J,et al.Supramolecular hydrogel microcapsules via cucurbit[8] uril host-guest interactions with triggered and UV-controlled molecular permeability[J].Chemical Science,2015,6(8):4929.
[5] APPEL E A,LOH X J,JONES S T,et al.Ultrahigh-water-content supramolecular hydrogels exhibiting multistimuli responsiveness[J].Journal of the American Chemical Society,2012,134(28):11767.
[6] YU X D,CHEN L M,ZHANG M M,et al.Low-molecular-mass gels responding to ultrasound and mechanical stress:towards self-healing materials[J].Chemical Society Reviews,2014,43(15):5346.
[7] DU X W,ZHOU J,SHI J F,et al.Supramolecular hydrogelators and hydrogels:from soft matter to molecular biomaterials[J].Chemical Reviews,2015,115(24):13165.
[8] BHUNIYA S,KIM B H.An insulin-sensing sugar-based fluorescent hydrogel[J].Chemical Communications,2006(17):1842.
[9] NYSTR?M G,FERNáNDES-RONCO M P,BOLISETTY S,et al.Amyloid templated gold aerogels[J].Advanced Materials,2016,28(3):472.
[10] GHOSH S,PRAVEEN V K,AJAYAGHOSH A.The chemistry and applications of π-gels[J].Annual Review of Materials Research,2016,46:235.
[11] DíAZ D D,KUHBECK D,KOOPMANS R J.Stimuli-responsive gels as reaction vessels and reusable catalysts[J].Chemical Society Reviews,2011,40(1):427.
[12] FOSTER J A,PIEPENBROCK M-O M,LLOYD G O,et al.Anion-switchable supramolecular gels for controlling pharmaceutical crystal growth[J].Nature Chemistry,2010,2(10):1037.
[13] BENDIKOV M,WUDL F.Tetrathiafulvalenes,oligoacenenes,and their buckminsterfullerene derivatives:the brick and mortar of organic electronics[J].Chemical Reviews,2004,104(11):4891.
[14] PEASE A R,JEPPESEN J O,STODDART J F,et al.Switching devices based on interlocked molecules[J].Accounts of Chemical Research,2001,34(6):433.
[15] NIELSEN M B,LOMHOLT C,BECHER J.Tetrathiafulvalenes as building blocks in supramolecular chemistry Ⅱ[J].Chemical Society Reviews,2000,29(3):153.
[16] PUIGMARTí-LUIS J,LAUKHIN V,PéREZ D,et al.Supramolecular conducting nanowires from organogels[J].Angewandte Chemie International Edition,2007,46(1-2):238.
[17] KITAHARA T,SHIRAKAWA M,KAWANO S,et al.Creation of a mixed-valence state from one-dimensionally aligned TTF utilizing the self-assembling nature of a low molecular-weight gel[J].Journal of the American Chemical Society,2005,127(43):14980.
[18] PUIGMARTí-LUIS J,LAUKHINA E E,LAUKHIN V N,et al.Rich phase behavior in a supramolecular conducting material derived from an organogelator[J].Advanced Functional Materials,2009,19(6):934.
[19] PUIGMARTí-LUIS J,PéREZ D,LAUKHIN V N,et al.Solvent effect on the morphology and function of novel gel-derived molecular materials[J].Journal of Materials Chemistry,2010,20(3):466.
[20] WANG C,CHEN Q,SUN F,et al.Multistimuli responsive organogels based on a new gelator featuring tetrathiafulvalene and azobenzene groups:reversible tuning of the gel-sol transition by redox reactions and light irradiation[J].Journal of the American Chemical Society,2010,132(9):3092.
[21] MITSUMOTO K,CAMERON J M,WEI R J,et al.A multi-redox responsive cyanometalate- based metallogel[J].Chemistry:A European Journal,2017,23(7):1502.
[22] LIU Y C,YIN Z R,JIN L Y,et al.Monopyrrolo- tetrathiafulvalene-based supramolecular organogels:multi-stimuli responsiveness and formation of charge- transfer salt gels[J].Dyes and Pigments,2017,140:500.