含二茂铁结构单元的阴离子受体的合成、表征及阴离子识别性能
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摘要
通过Steglich酯化反应,利用二茂铁甲酸与2-羟基-3,6,7,10,11-五己氧基苯并菲反应,得到含有酯基二茂铁侧链的阴离子受体二茂铁甲酸-3,6,7,10,11-五己氧基苯并菲酯(R2-1),并通过红外光谱、核磁共振氢谱进行表征。利用电化学方法考察了R2-1与阴离子客体之间的相互作用。结果表明:R2-1在乙腈中对H_2PO_4~-、AcO~-和F~-有较好的识别效果,有明显的电化学信号。F~-与R2-1的结合主要依靠静电作用;AcO~-和H_2PO_4~-与R2-1的结合受到氢键和静电作用的双重影响,其中AcO~-与R2-1的结合,静电作用占主导地位,H_2PO_4~-与R2-1的结合,氢键占主导地位。
By Steglich esterification reaction between the ferrocenecarboxylic acid and 2-hydroxy-3,6,7,10,11-pentahexyloxybenzophenanthrene, the anion receptor ferrocene carboxylic acid-3, 6, 7, 10, 11-pentahexyloxybenzophenanthrene(R2-1) containing ester group-ferrocene side chain was synthesized,and its structure was characterized by IR and ~1H-NMR.The interaction between R2-1 and the anion guest was studied by the electrochemical method.The results showed that R2-1 had a good recognition performance on H_2PO_4~-,AcO~- and F~- in acetonitrile and had obvious electrochemical signal.The combination of F~- and R2-1 mainly relied on electrostatic interaction;while the combination of AcO~- or H_2PO_4~- with R2-1 were affected by both hydrogen bond and electrostatic interaction.Among them,the coordination of AcO~- and R2-1 was dominated by electrostatic interaction,whereas the coordination of H_2PO_4~- and R2-1 was dominated by hydrogen bond.
By Steglich esterification reaction between the ferrocenecarboxylic acid and 2-hydroxy-3,6,7,10,11-pentahexyloxybenzophenanthrene, the anion receptor ferrocene carboxylic acid-3, 6, 7, 10, 11-pentahexyloxybenzophenanthrene(R2-1) containing ester group-ferrocene side chain was synthesized,and its structure was characterized by IR and ~1H-NMR.The interaction between R2-1 and the anion guest was studied by the electrochemical method.The results showed that R2-1 had a good recognition performance on H_2PO_4~-,AcO~- and F~- in acetonitrile and had obvious electrochemical signal.The combination of F~- and R2-1 mainly relied on electrostatic interaction;while the combination of AcO~- or H_2PO_4~- with R2-1 were affected by both hydrogen bond and electrostatic interaction.Among them,the coordination of AcO~- and R2-1 was dominated by electrostatic interaction,whereas the coordination of H_2PO_4~- and R2-1 was dominated by hydrogen bond.
引文
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[3]LIU J,YAN J L,YUAN X W,et al.A novel lowmolecular-mass gelator with a redox active ferrocenyl group:Tuning gel formation by oxidation[J].Journal of Colloid and Interface Science,2008,318(2):397-404.
[4]陈哲夫.含二茂铁基和偶氮苯基席夫碱化合物的合成、性能及在阴离子识别中的应用研究[D].杭州:浙江大学,2013.
[5]李根,王玉慧,李明明,等.二茂铁衍生物的研究进展[J].辽宁化工,2013,42(6):631-634.
[6]DESCALZO A B,RURACK K,WEISSHOFF H,et al.Rational design of a chromo-and fluorogenic hybrid chemosensor material for the detection of long-chain carboxylates[J].Journal of the American Chemical Society,2005,127(1):184-200.
[7]孔翔飞.盘状液晶苯并菲类光电材料的合成及表征[D].北京:北京交通大学,2011.
[8]ADAM D,CLOSS F,FREY T,et al.Transient photoconductivity in a discotic liquid crystal[J].Physical Review Letters,1993,70(4):457-460.
[9]赵可清,杨高帆,余文浩,等.盘状液晶中间体单羟基苯并菲简便合成[J].有机化学,2009,29(12):2017-2020.
[10]BEER P D,HAYES E J.Transition metal and organometallic anion complexation agents[J].Coordination Chemistry Reviews,2003,240(1/2):167-189.
[11]SUN R L,WANG L,YU H J,et al.Molecular recognition and sensing based on ferrocene derivatives and ferrocene-based polymers[J].Organometallics,2014,33(18):4560-4573.
[12]吴辉煌.应用电化学基础[M].厦门:厦门大学出版社,2006.
[13]胡会利,李宁.电化学测量[M].北京:国防工业出版社,2007.
[14]CAO Q Y,HAN Y M,YAO P S,et al.A new ferrocene-anthracene dyad bearing amide and triazolium donors for dual-signaling sensing to anions[J].Tetrahedron Letters,2014,55(1):248-251.
[15]HEINZE J.Cyclic voltammetry-“electrochemical spectroscopy”.New analytical methods(25)[J].Angewandte Chemie International Edition,1984,23(11):831-847.
[16]GALE P A,CHEN Z,DREW M G B,et al.Lowerrim ferrocenyl substituted calixarenes:New electrochemical sensors for anions[J].Polyhedron,1998,17(4):405-412.
[17]ALFONSO M,TáRRAGA A,MOLINA P.Ferrocenylbenzobisimidazoles for recognition of anions and cations[J].Inorganic Chemistry,2013,52(13):7487-7496.
[18]BAYLY S R,BEER P D.Metal-based anion receptor systems[J].Structure and Bond,2008,129:45-94.
[19]马亮.新型含酰胺基和酯基的二茂铁基化合物的合成、性能及应用研究[D].杭州:浙江大学,2011.
[20]TSIERKEZOS N G.Cyclic voltammetric studies of ferrocene in nonaqueous solvents in the temperature range from 248.15to 298.15K[J].Journal of Solution Chemistry,2007,36(3):289-302.
[21]翁潭清.二茂铁烷基咪唑类化合物的合成、表征及其电化学行为研究[D].武汉:华中师范大学,2009.