[超分子化学与晶体工程基础]-晶体工程.pptxVIP

3. 晶体工程Crystal Engineering“One of the continuing scandals in the physical sciences is thatit remains in general impossible to predict the structure of eventhe simplest crystalline solids from a knowledge of their chemical composition.”——J. Maddox, Nature, 1988, 335, 201.Crystal Engineering is “the understanding of intermolecular interactions in the context of crystal packing and the utilization of such understanding in the design of new solids with desired physical and chemical properties.”认识晶体堆积中的分子间相互作用力，以及利用这些认识去设计具有特定物理和化学性质的新晶体。——G. R. Desiraju, 1988Crystal Engineering Supramolecular synthons晶体工程的目的：认识和设计足够结实的合成子，以保证普适性和可预测性，从 而通过分子间作用，形成所预期的1、2、3维结构。通过分子堆积，设计和制出 奇特新颖、花样繁多、具有特定性质的新晶体。The goal of crystal engineering is to recognize and design synthons that are robust enough, which ensures generality and predictability. Such structural predictability leads, in turn, to the anticipation of one-, two-, and three-dimensional patterns formed with intermolecular interactions.超分子合成子：指超分子中的结构单元，这些结构单元可以通过已知或者可能想 到的，包含超分子作用的合成操作而形成，并组装起来。Supramolecular synthons are structural units within supramolecules which can be formed and/or assembled by known or conceivable synthetic operations involving intermolecular interactions. (by Desiraju).Supramolecular synthons：超分子组装的结构基元一些基于氢键作用的超分子合成子羧酸氢键对是最常用的超分子合成子氢键：方向性、饱和性、强度……基于氢键的晶体工程1. Organic Donors and Acceptors for H-bondinggood donors:bad donors:ROH, RNH2, C-H,good acceptors:bad acceptors:基于氢键的晶体工程Basic properties of H-bondsHow many H-bonds can be formed?sp3sp2 and sp3 hybridizationsp2overlap of a sp2/sp3 orbital with a proton(2) Directional, reversible (association/dissociation), designable(1) 0-Dimensional (0-D) ExamplesynthonCrystal structure(2) 1-Dimensional (1-D) ExamplesynthonCrystal structure(3) 2-Dimensional (2-D) ExampleHOOHoneycomb networkobserved for BTC):(a) H-bonding patternOH O(b) the hexagonal channels蜂窝状网Guest: isooctane正辛烷space-filling model :van der Waals’ radiiHerbstein, F. H.; et al. J. Inclusion