基于苯并咪唑的超分子金属有机凝胶及其刺激响应性能研究
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摘要
合成了一种基于羧基功能化的苯并咪唑类有机凝胶因子(C11).该凝胶因子在水-乙醇体系中不仅能自组装成超分子有机凝胶(C11-OG),而且与银离子络合后可以自组装成具有多重刺激响应性能的金属凝胶(Ag-MG).有机凝胶C11-OG和金属凝胶Ag-MG都具有凝聚态荧光增强(AIEE)的性能.金属凝胶Ag-MG可对温度、EDTA和Na_2S的刺激进行可逆的溶液-凝胶变化响应及荧光响应.此外,通过扫描电镜(SEM)、X射线衍射(XRD)和红外光谱(FT-IR)研究了其刺激响应机理.
In this paper,a simple carboxylic-functionalized benzimidazole gelator(C11)is prepared.This gelator can self-assembled to supramolecular organogel and metallogel(C11-OG and Ag-MG)in EtOH-H_2 O with multi-stimuli responsive properties.Besides,the organogel C11-OG and metallogel Ag-MG have dramatic aggregation-induced fluorescence emission enhancement(AIEE).The Ag-MG reveals outstanding reversible sol-gel transitions and fluorescent changes induced by changing of temperature,EDTA and Na_2 S.In addition,the stimuli-responsive mechanism is tested by SEM,XRD and FT-IR.
In this paper,a simple carboxylic-functionalized benzimidazole gelator(C11)is prepared.This gelator can self-assembled to supramolecular organogel and metallogel(C11-OG and Ag-MG)in EtOH-H_2 O with multi-stimuli responsive properties.Besides,the organogel C11-OG and metallogel Ag-MG have dramatic aggregation-induced fluorescence emission enhancement(AIEE).The Ag-MG reveals outstanding reversible sol-gel transitions and fluorescent changes induced by changing of temperature,EDTA and Na_2 S.In addition,the stimuli-responsive mechanism is tested by SEM,XRD and FT-IR.
引文
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[42]WANG Ke-Fei,JIAN Fang-fang,ZHUANG Rui-rui,et al.New ionic liquids of N,N′-dialkylbenzimidazolium salt comprising copper(Ⅱ)ions[J].Crystal Growth&Design,2009,9(3):1474.
[2]RAN Xia,WANG Hai-tao,ZHANG Peng,et al.Photo-induced fiber-vesicle morphological change in an organogel based on an azophenyl hydrazide derivative[J].Soft Matter,2011,7:8561.
[3]BAIRI P,CHAKRABORTY P,SHIT A,et al.A co-assembled gel of a pyromellitic dianhydride derivative and polyaniline with optoelectronic and photovoltaic properties[J].Langmuir,2014,30:7547.
[4]MA Xin-xian,YU Da-wei,TANG Ning,et al.Tb3+-containing supramolecular hydrogels:luminescence properties and reversible sol-gel transitions induced by external stimuli[J].Dalton Trans,2014,43:9856.
[5]杨美妮,晏妮,何刚,等.一种含芘葡萄糖衍生物的合成及其胶凝行为[J].物理化学学报,2009,25(6):1040.
[6]KOTOVA O,DALY R,SANTOS C M G D,et al.Cross-linking the fibers of supramolecular gels formed from a tripodal terpyridine derived ligand with d-block metal ions[J].Inorg Chem,2015,54:7735.
[7]HUANG Fei-he,SCHERMAN O A.Supramolecular polymers[J].Chem Soc Rev,2012,41(18):5879.
[8]YU Guo-can,YAN Xu-zhou,HAN Cheng-you,et al.Characterization of supramolecular gels[J].Chem Soc Rev,2013,42(16):6697.
[9]ZENG Ji-sen,WANG Wei,DENG Peng-chi,et al.Interplay of olefin metathesis and multiple hydrogen bonding interactions:covalently cross-linked zippers[J].Org Lett,2011,13(15):3798.
[10]MA Yuan,MA Heng-chang,YANG Zen-ming,et al.Methyl cinnamate-derived fluorescent rigid organogels based on cooperativeπ-πstacking and C=O…πinteractions instead of H-bonding and alkyl chains[J].Langmuir,2015,31:4916.
[11]JAMES A J,PERRIN A,JONES C D,et al.Highly interlocked anion-bridged supramolecular networks from interrupted imidazole-urea gels[J].Chem Commun,2014,50:12851
[12]SIVADAS A P,SALEESH K N S,PRABHU D D,et al.Supergelation via purely aromaticπ-πdriven self-assembly of pseudodiscotic oxadiazole mesogens[J].J Am Chem Soc,2014,136(14):5416.
[13]SENGUPTA S,MONDAL R.A novel gel-based approach to wastewater treatment-unique one-shot solution to potentially toxic metal and dye removal problems[J].J Mater Chem A,2014,2:16373.
[14]RODRIGUES M,CALPENA A C,AMABILINO D B,et al.Supramolecular gels based on a gemini imidazolium amphiphile as molecular material for drug delivery[J].J Mater Chem B,2014,2:5419.
[15]SARKAR S,DUTTA S,CHAKRABARTI S,et al.Redox-switchable copper(Ⅰ)metallogel:a metal-organic material for selective and naked-eye sensing of picric acid[J].ACS Appl Mater Interfaces,2014,6:6308.
[16]YANG Dong,LIU Chang-xia,ZHANG Li,et al.Visualized discrimination of ATP from ADP and AMP through collapse of supramolecular gels[J].Chem Commun,2014,50:12688.
[17]GANTA S,CHAND D K.Nanoscale metallogel via self-assembly of self-assembled trinuclear coordination rings:multi-stimuli-responsive soft materials[J].Dalton Trans,2015,44:15181.
[18]FAN Kai-qi,YANG Jun,WANG Xiao-bo,et al.Rational construction of gel-based supramolecular logic gates by using a functional gelator with multiplestimuli responsive properties[J].Soft Matter,2014,10:8370.
[19]LI Yi-bao,CHENG LIN-xiu,LIU Chun-hua,et al.Hierarchical self-assembly of amino acid derivatives into stimuli-responsive luminescent gels[J].Soft Matter,2014,10:8261.
[20]CHEN Pang-kuan,LI Qiao-chu,GRINDY S,et al.White light emitting lanthanide metallogels with tunable luminescence and reversible stimuliresponsive properties[J].J Am Chem Soc,2015,137:11590.
[21]陈凯,金鑫,唐黎明.超分子金属凝胶[J].化学进展,2010,22(6):1094.
[22]BARMAN S,GARG J A,BLACQUE O,et al.Triptycene based luminescent metal-organic gels for chemosensing[J].Chem Commun,2012,48:11127.
[23]TAM A,YAM V W.Recent advances in metallogels[J].Chem Soc Rev,2013,42:1540.
[24]PARK S H,JUNG S H,AHN J,et al.Reversibly tunable helix inversion in supramolecular gels trigged by Co2+[J].Chem Commun,2014,50:13495.
[25]吴源.纳米银的生物效应及毒性作用机制[D].合肥:中国科学技术大学,2010.
[26]BAIRI P,ROY B,NANDI A K.pH and anion sensitive silver(Ⅰ)coordinated melamine hydrogel with dye absorbing properties:metastability at low melamine concentration[J].J Mater Chem,2011,21:11747.
[27]ZHANG You-ming,YOU Xing-mei,YAO Hong,et al.A silver-induced metal-organic gel based on biscarboxyl-functionalised benzimidazole derivative:stimuli responsive and dye sorption[J].Supramolecular Chemistry,2014,26(1):39.
[28]张有明,李海龙,杨青平,等.对氟离子选择性识别的小分子有机凝胶的合成[J].西北师范大学学报(自然科学版),2015,51(1):53.
[29]YAO Hong,YOU Xing-mei,LIN Qi,et al.Multistimuli responsive metal-organic gel of benzimidazolbased ligands with lead nitrate and their use in removal of dyes from waste-water[J].Chinese Chemical Letters,2013,24:703.
[30]ZHANG You-ming,ZHANG Wan-qiang,LI Junqiang,et al.Cadmium-induced supramolecular hydrogels:reversible sol-gel transitions induced by EDTA and acid/base exchange[J].Materials Letters,2012,82:227.
[31]张有明,刘勇,林奇,等.具有新颖嵌合作用的金属配合物的微波合成、晶体结构及性质研究[J].中国科学:化学,2011,41(5):869.
[32]YAO Hong,YOU Xing-mei,LIN Qi,et al.Metal-organic gels based on carboxyl-functionalized benzimidazole and their stimuli responsivenesses[J].Chinese Journal of Chemistry,2014,32(7):607.
[33]LIN Qi,SUN Bin,YANG Qing-ping,et al.A novel strategy for the design of smart supramolecular gels:controlling stimuli-response properties through competitive coordination of two different metal ions[J].Chem Commun,2014,50:10669.
[34]MAITY A,ALI F,AGARWALLA H,et al.Tuning of multiple luminescence outputs and whitelight emission from a single gelator molecule through an ESIPT coupled AIEE process[J].Chem Commun,2015,51:2130.
[35]LIN Qi,SUN Bin,YANG Qing-ping,et al.Double metal ions competitively control the guestsensing process:a facile approach to stimuliresponsive supramolecular gels[J].Chem Eur J,2014,20:1.
[36]POOL W O,HARWOOD H J.2-alkylbenzimidazoles as derivatives for the identification of aliphatic acids[J].J Am Chem Soc,1937,59:178.
[37]LAN Y,CORRADINI M G,WEISS R G,et al.To gel or not to gel:correlating molecular gelation with solvent parameters[J].Chem Soc Rev,2015,44:6035.
[38]LIN Qi,ZHU Xin,FU Yong-peng,et al.Rationally designed anion-responsive-organogels:sensing F-via reversible color changes in gel-gel states with specific selectivity[J].Soft Matter,2014,10:5715.
[39]LIN Qi,YANG Qing-ping,SUN Bin,et al.Competitive coordination control the AIE and micro states of supramolecular gel:an efficient approach for reversible dual-channel stimuli-response materials[J].Soft Matter,2014,10(42):8427.
[40]DIAS H V R,DIYABALANAGE H V K.Trimeric silver(Ⅰ)pyrazolates with isopropyl,bromo,and nitro substituents:synthesis and characterization of{[3,5-(i-Pr)2Pz]Ag}3,{[3,5-(i-Pr)2,4-(Br)Pz]Ag}3,and{[3,5-(i-Pr)2,4-(NO2)Pz]Ag}3[J].Polyhedron,2006,25:1655.
[41]WEI Kai-ju,NI jia,LIU Yang-zhong.Heterobimetallic metal-complex assemblies constructed from the flexible arm-like ligand 1,1′-bis[(3-pyridylamino)carbonyl]ferrocene:structural versatility in the solid state[J].Inorg Chem,2010,49:1834.
[42]WANG Ke-Fei,JIAN Fang-fang,ZHUANG Rui-rui,et al.New ionic liquids of N,N′-dialkylbenzimidazolium salt comprising copper(Ⅱ)ions[J].Crystal Growth&Design,2009,9(3):1474.