摘要
和其它类型的分子间作用力相比,氢键具有可逆性、方向性和作用强度可调控性等突出特点,因此氢键在超分子化学及材料科学领域均引起了广泛关注。但是从目前报道的文献来看,只有AADD-DDAA和ADDA-DAAD四重氢键组装体系能够成功用于构筑超分子聚合物并应用于相关材料科学中,而AAA-DDD三重氢键体系却几乎没有报道,主要原因是由于氢键受体AAA难以功能化而且合成难度相对较大。我们提出了一种合成可功能化的3,8-二苯基取代AAA受体的新路线并成功地将此路线应用于三重氢键组装超分子聚合物BisA AA-Bis DDD的构筑。通过荧光滴定、单晶培养以及~1H NMR滴定等表征方法对AAA-DDD三重氢键组装体系进行系统的表征,证明了我们设计的氢键组装体系之间能够发生组装。此外,我们在AAA和DDD合成方法的基础上进一步对AAA与DDD进行衍生设计合成了三重氢键组装聚合物单体Bis AAA与Bis DDD。通过对BisA AA-BisD DD超分子聚合物进行~1H NMR滴定、~1H NOESY谱分析、特性黏度测定以及聚合物粒度等表征证明了我们合成的超分子聚合物单体能够成功地发生组装。
For a complementary hydrogen-bonded complex,when every hydrogen-bonded acceptor is on one side and every hydrogen-bonded donor is on the other one,all the secondary interactions are attractive and the complex is highly stable.AAA-DDD is considered the most stable among triply hydrogen-bonded sequences.The easily synthesized and further derived AAA-DDD system is very desirable for hydrogen-bonded functional materials.In our case,AAA and DDD started from 4-methoxybenzaldehyde are synthesized with the Hantzsch pyridine synthesis and Friedlnder annulation reaction.The association constant determined by fluorescence titration in chloroform at room temperature is 2.09 × 10~7 M~(-1).AAA and DDD components are not coplanar but form a V-shape in the solid state.We have also developed supramolecular polymers based on AAA-DDD triply hydrogen bonds.This work may make AAA-DDD triply hydrogen-bonded sequences easily accessible for stimuli-responsive materials.
引文
[1]S.Djurdjevic,D.A.Leigh,H.McN ab,S.Parsons,G.Teobaldi,F.Zerbetto,J.Am.Chem.Soc.2007,129,476.
[2]B.A.Blight,A.Camara-Campos,S.Djurdjevic,M.Kaller,D.A.Leigh,F.M.Mc Millan,H.McN ab,A.M.Z.Slawin,J.Am.Chem.Soc.2009,131,14116.
[3]Y.-F.Han,W.-Q.Chen,H.-B.Wang,*Y.-X.Yuan,N.-N.Wu,X.-Z.Song,L.Yang.Chem.Eur.J.2014,20,16980.
