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Diffraction for chemical reactions: gas uptake and extrusion in non-porous crystals

化学反应的衍射：无孔晶体中的气体吸收和挤出

基本信息

批准号：
EP/F02195X/1
负责人：
Lee Brammer
金额：
$ 20.74万
依托单位：
University of Sheffield
依托单位国家：
英国
项目类别：
Research Grant
财政年份：
2008
资助国家：
英国
起止时间：
2008 至无数据
项目状态：
已结题

来源：
https://gtr.ukri.org/projects?ref=EP%2FF02195X%2F1
关键词：
Diffraction chemical reactions gas uptake

项目摘要

Although uptake or release of gases by porous solids is well established and can even occur in materials that remain crystalline during such processes, analogous uptake and release of gases by non-porous crystalline materials is very rare and extremely poorly understood. The implication, of course, is that significant flexibility is required within a solid where molecules are tightly packed together in order to permit even small molecules to enter from the gas phase, or to be released if trapped.The proposed project builds upon preliminary results that provide a proof-of-concept for three families of crystalline materials that are able to either absorb or release small molecules such as hydrogen halides, molecular iodine or alcohols. These processes are in fact chemical reactions that require in most instances major changes in covalent bonding and in molecular geometry within the crystalline solid. Despite these movements of molecules and the formation or breaking of strong bonds, these families of materials retain their crystallinity. This makes them ideal for study by diffraction methods, which can provide detailed geometric information on the molecular structures within the crystals. In particular synchrotron X-ray radiation will be used, employing the methods of single crystal and powder diffraction to chart the progress of these reactions and to conduct systematic studies within each family of materials that will permit details of the mechanism of these unusual reactions to be revealed. These experiments will be combined with infra red spectroscopic measurements that can be used to monitor the gases and single crystal neutron diffraction which will be used to obtain particularly accurate geometries from crystals in cases where hydrogen atoms play a key role in the reactions. The results will be of great fundamental importance in understanding the behaviour of molecular materials, specifically their ability to undergo dynamic behaviour and even chemical reactions. This will be of value to a wide range of scientists engaged in designing molecular materials. The reactions studied are also believed to be related to processes such a hydration/dehydration of molecular crystals which are of great commercial interest to the pharmaceutical industry which formulates many drugs in crystalline form and for which efficacy can depend greatly on the particular crystalline form.

虽然多孔固体吸收或释放气体是公认的，甚至可以发生在材料中，保持结晶在这样的过程中，类似的吸收和释放气体的非多孔结晶材料是非常罕见的和知之甚少。当然，这意味着在分子紧密堆积在一起的固体中需要显著的灵活性，以允许即使是小分子也能从气相进入，或者在被困时被释放。拟议的项目建立在初步结果的基础上，这些结果为三个家族的晶体材料提供了概念验证，这些晶体材料能够吸收或释放小分子，如卤化氢，分子碘或醇。这些过程实际上是化学反应，在大多数情况下需要结晶固体内共价键和分子几何结构的重大变化。尽管这些分子运动和强键的形成或断裂，这些材料家族仍保持其结晶度。这使得它们非常适合通过衍射方法进行研究，该方法可以提供晶体内分子结构的详细几何信息。特别是同步加速器X射线辐射将被使用，采用单晶和粉末衍射的方法来绘制这些反应的进展，并在每个材料家族内进行系统的研究，以揭示这些不寻常反应的机制的细节。这些实验将与红外光谱测量相结合，可以用来监测气体和单晶中子衍射，这将用于获得特别精确的几何形状，从晶体中的氢原子在反应中发挥关键作用的情况下。这些结果对于理解分子材料的行为，特别是它们进行动态行为甚至化学反应的能力具有重要的基础意义。这将对从事分子材料设计的广泛科学家具有价值。所研究的反应也被认为与诸如分子晶体的水合/脱水的过程有关，这对制药工业具有很大的商业利益，制药工业以结晶形式配制许多药物，并且其功效可以很大程度上取决于特定的结晶形式。

项目成果

期刊论文数量（9）

专著数量（0）

科研奖励数量（0）

会议论文数量（0）

专利数量（0）

Ag-channel-MOF_30Oct16_SI.pdf from Arene guest selectivity and pore flexibility in a metal-organic framework with semi-fluorinated channel walls

Ag-channel-MOF_30Oct16_SI.pdf，来自具有半氟化通道壁的金属有机框架中的芳烃客体选择性和孔隙灵活性

DOI：
10.6084/m9.figshare.4236389
发表时间：
2016
期刊：
影响因子：
0
作者：
Smith R
通讯作者：
Smith R

Crystallographic studies of gas sorption in metal-organic frameworks.

DOI：
10.1107/s2052520614009834
发表时间：
2014-06
期刊：
Acta crystallographica Section B, Structural science, crystal engineering and materials
影响因子：
0
作者：
Carrington EJ;Vitórica-Yrezábal IJ;Brammer L
通讯作者：
Brammer L

Solvent-vapour-assisted pathways and the role of pre-organization in solid-state transformations of coordination polymers.

DOI：
10.1107/s2052252515000147
发表时间：
2015-03-01
期刊：
IUCrJ
影响因子：
3.9
作者：
Wright JS;Vitórica-Yrezábal IJ;Adams H;Thompson SP;Hill AH;Brammer L
通讯作者：
Brammer L

Coordination polymer flexibility leads to polymorphism and enables a crystalline solid-vapour reaction: a multi-technique mechanistic study.

DOI：
10.1002/chem.201500514
发表时间：
2015-06-08
期刊：
Chemistry (Weinheim an der Bergstrasse, Germany)
影响因子：
0
作者：
Vitórica-Yrezábal IJ;Libri S;Loader JR;Mínguez Espallargas G;Hippler M;Fletcher AJ;Thompson SP;Warren JE;Musumeci D;Ward MD;Brammer L
通讯作者：
Brammer L

Solid state supramolecular chemistry : gas-solid reactions and intermolecular interactions

固态超分子化学：气固反应和分子间相互作用