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Host–Guest Interactions of Sodiumsulfonatomethyleneresorcinarene and Quaternary Ammonium Halides: An Experimental–Computational Analysis of the Guest Inclusion Properties
Crystal Growth & Design ( IF 3.2 ) Pub Date : 2020-01-15 , DOI: 10.1021/acs.cgd.9b01540 Kwaku Twum 1 , J. Mikko Rautiainen 2 , Shilin Yu 2 , Khai-Nghi Truong 2 , Jordan Feder 1 , Kari Rissanen 2 , Rakesh Puttreddy 2, 3 , Ngong Kodiah Beyeh 1
Crystal Growth & Design ( IF 3.2 ) Pub Date : 2020-01-15 , DOI: 10.1021/acs.cgd.9b01540 Kwaku Twum 1 , J. Mikko Rautiainen 2 , Shilin Yu 2 , Khai-Nghi Truong 2 , Jordan Feder 1 , Kari Rissanen 2 , Rakesh Puttreddy 2, 3 , Ngong Kodiah Beyeh 1
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The molecular recognition of nine quaternary alkyl- and aryl-ammonium halides (Bn) by two different receptors, Calkyl-tetrasodiumsulfonatomethyleneresorcinarene (An), were studied in solution using 1H NMR spectroscopy. Substitution of methylenesulfonate groups at 2-positions of resorcinol units resulted in an increase of cavity depth by ∼2.80 Å and a narrow cavity portal compared to Calkyl-2-H-resorcinarenes. The effect of alkyl chain lengths on the endo-complexation, that is the ability to incorporate other than N-methyl chains inside the cavities, was investigated using ammonium cations of the type +NH2(R1)(R2), (R1 = Me, Et, Bu, R2 = Bu, Ph, Bz). The C–H···π interactions between guests and hosts are the key driving forces for 14 out of 16 observed endo-complexes. In the case of the N-butyl-N-benzylammonium cation, the hydrogen bonding between -NH2 and sulfonate oxygens and the larger size hamper the N-butyl and N-benzyl groups from entering the host cavity. Association constants derived from isothermal calorimetry titrations confirm 1:1 host–guest complexes highlighting guest affinity, based on size and orientation. X-ray crystallographic analysis revealed two types of complexes viz. sodium-containing cocrystals, [(An)4–·m(Bn)+·qNa+], and sodium-free, [(An)4–·4(Bn)+]. Both types accommodate (Bn+) guests in their cavities. The N-methylated heterocycle guests and host form capsule-like structures in which the two halves were joined by O–Na coordination bonds and self-assembly into two-dimensional polymeric sheets. From the crystal structures, different conformations of methylenesulfonate groups with respect to cavity arising due to tetrahedral geometry of methylene linker were observed. Density functional theory (DFT) computations were used to analyze the effects of endo-guests on host conformations and to estimate the relative strengths of host–guest interactions.
中文翻译：
磺酰胺基亚甲基间苯二甲酸钠和卤化季铵的宿主-客体相互作用：客体包裹体性质的实验-计算分析
九季烷基和芳基卤化铵（分子识别BN由两个不同的受体），C烷基-tetrasodiumsulfonatomethyleneresorcinarene（一种），在使用溶液进行了研究1个H NMR光谱。与C -2-烷基-H-间苯二酚芳烃相比，间苯二酚单元2位上的亚磺酸酯基取代可导致腔深度增加约2.80Å，且腔孔狭窄。使用+ NH 2（R 1）型铵阳离子研究了烷基链长度对内复合物的影响，即在腔体内掺入除N-甲基以外的链的能力。）（R 2），（R 1 = Me，Et，Bu，R 2 = Bu，Ph，Bz）。客体与宿主之间的CH-···π相互作用是观察到的16种内复合物中的14种的关键驱动力。在的情况下Ñ丁基- Ñ -benzylammonium阳离子，-NH之间的氢键键合2个和磺酸氧较大尺寸妨碍Ñ丁基和Ñ进入宿主腔苄基的基团。从等温量热法滴定得出的缔合常数证实了1：1主客体复合物，突出了客体的亲和力（基于大小和方向）。X射线晶体学分析显示两种类型的配合物。含钠共晶体，[（一种）4 – · m（Bn）+ · q Na + ]和无钠，[（An）4 – ·4（Bn）+ ]。两种类型的腔中都可容纳（Bn +）客人。该ñ-甲基化的杂环客体和宿主形成胶囊状结构，其中两半通过O-Na配位键连接并自组装成二维聚合物片。从晶体结构，观察到由于亚甲基接头的四面体几何形状而引起的关于腔的亚磺酸酯基的不同构象。密度泛函理论（DFT）计算被用来分析客体对宿主构象的影响，并估计客体相互作用的相对强度。
更新日期：2020-01-15
中文翻译：
磺酰胺基亚甲基间苯二甲酸钠和卤化季铵的宿主-客体相互作用：客体包裹体性质的实验-计算分析
九季烷基和芳基卤化铵（分子识别BN由两个不同的受体），C烷基-tetrasodiumsulfonatomethyleneresorcinarene（一种），在使用溶液进行了研究1个H NMR光谱。与C -2-烷基-H-间苯二酚芳烃相比，间苯二酚单元2位上的亚磺酸酯基取代可导致腔深度增加约2.80Å，且腔孔狭窄。使用+ NH 2（R 1）型铵阳离子研究了烷基链长度对内复合物的影响，即在腔体内掺入除N-甲基以外的链的能力。）（R 2），（R 1 = Me，Et，Bu，R 2 = Bu，Ph，Bz）。客体与宿主之间的CH-···π相互作用是观察到的16种内复合物中的14种的关键驱动力。在的情况下Ñ丁基- Ñ -benzylammonium阳离子，-NH之间的氢键键合2个和磺酸氧较大尺寸妨碍Ñ丁基和Ñ进入宿主腔苄基的基团。从等温量热法滴定得出的缔合常数证实了1：1主客体复合物，突出了客体的亲和力（基于大小和方向）。X射线晶体学分析显示两种类型的配合物。含钠共晶体，[（一种）4 – · m（Bn）+ · q Na + ]和无钠，[（An）4 – ·4（Bn）+ ]。两种类型的腔中都可容纳（Bn +）客人。该ñ-甲基化的杂环客体和宿主形成胶囊状结构，其中两半通过O-Na配位键连接并自组装成二维聚合物片。从晶体结构，观察到由于亚甲基接头的四面体几何形状而引起的关于腔的亚磺酸酯基的不同构象。密度泛函理论（DFT）计算被用来分析客体对宿主构象的影响，并估计客体相互作用的相对强度。
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