Dynamic Aspects of Lattice Inclusion Complexation Involving a Phase Change. Equilibrium, Kinetics, and Energetics of Guest-Binding to a Hydrogen-Bonded Flexible Organic Network
Dynamic Aspects of Lattice Inclusion Complexation Involving a Phase Change. Equilibrium, Kinetics, and Energetics of Guest-Binding to a Hydrogen-Bonded Flexible Organic Network
复制标题
涉及相变的晶格包含络合的动态方面。
DOI：
10.1021/ja9812453
复制
发表时间：
1998
影响因子：
15
通讯作者：
Y. Aoyama
中科院分区：
文献类型：
--
作者：
Takehisa Dewa;K. Endo;Y. Aoyama
用压力衰减法、X-射线粉末衍射法和重量/热解吸法研究了主客体(1)与乙酸乙酯的固气络合反应。它涉及一个放热(∼30千卡/摩尔)相变，并在客体蒸汽的临界(平衡)压力下表现出“垂直”吸附和解吸“等温线”。这符合二组分/三相/单自由度系统的相律。吸附活化能为2.3千卡/摩尔，脱附活化能为34千卡/摩尔；在25℃脱附需要数周时间。乙酸乙酯加合物的晶体结构说明了主体1的柔性氢键网络如何调整自己以适应小客体。其他极性客体(酯、酮和醇)的行为类似，并产生抗解吸的稳定加合物，除了酯和酮客体中体积最小的成员，即乙酸甲酯和丙酮。其相变机理为……
The solid/gas complexation of anthracenebisresorcinol host (1) and ethyl acetate as a guest was monitored by pressure-decay, X-ray powder diffraction, and gravimetric/calorimetric thermal desorption analyses. It involves an exothermic (∼30 kcal/mol) phase transition and exhibits “vertical” adsorption as well as desorption “isotherms” at a threshold (equilibrium) pressure (Pth) of the guest vapor. This is in accord with the phase rule for a two-component/three-phase/one-freedom system. The activation energies of adsorption and desorption are 2.3 and 34 kcal/mol, respectively; desorption at 25 °C takes weeks. The crystal structure of the ethyl acetate adduct illustrates how the flexible hydrogen-bonded network of host 1 adjusts itself to the small guest. Other polar guests (ester, ketone, and alcohol) behave similarly and give rise to desorption-resistant stable adducts, except for the least bulky members of the ester and ketone guests, i.e., methyl acetate and acetone. The mechanism of phase transition is ...