New Chemistry of CTC-based Cavitands and Cryptophanes - Spin-Transition Switches, Near-IR Absorbers and Hosts for Gases

基于 CTC 的空配体和 Cryptophanes 的新化学 - 自旋跃迁开关、近红外吸收体和气体主体

• 批准号: EP/F040547/1
• 负责人: Malcolm Halcrow
• 金额: $ 26.67万
• 依托单位: University of Leeds
• 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%2FF040547%2F1
• 关键词: New; Chemistry; CTC; based; Cavitands

Cyclotriveratrylene ('CTV') is a rigid cyclic molecule with a shallow bowl shape, that has a well-established ability to bind other molecules in its cavity. While solvents and other small organic molecule guests can be accommodated, CTV is particularly notable for its ability to bind to fullerene (C60) and other spherical or globular compounds. As such, CTV is a prototypical example of an important class of supramolecular host known as the cavitands; that is, molecules with guest-accessible cavities. Cyclotriguaiacyclene (CTC), the title compound of this proposal, is a slightly cut-down version of CTV with the same rigid bowl shape.This proposal involves an extension of CTV chemistry into several new areas. First, is by preparing chemically modified derivatives of CTV with oxidisable functionalities, disposed in such a way as to bind metal ions around the edge of the molecular bowl. Precedent suggests that the bowl-shaped cavitand might be easily oxidised under these conditions, yielding metal-stabilised free radical products. Of particular interest will be to determine whether the radical centres can hop around the bowl. If they can, that would make the compounds strongly absorb infra-red radiation. If so, the next step would be to investigate ways of switching that IR absorption on and off. That might be done electrochemically or, in appropriately designed materials, by warming it up or cooling it down. Switchable near-IR absorbers like these can be very useful in fibre-optic communications devices.Binding metal centres to the periphery of CTV will also have the effect of substantially extending its cavity, more than doubling its diameter. We will also investigate these new enlarged cavitands as hosts for small and large organic guests. Of particular interest will be the effects of in-cavity guest binding on the light absorption and switching phenomena mentioned in the previous paragraph.We will also link two CTV bowls, on top of each other, to make new capsule molecules. There are two ways we will seek to do this. If we use metal ion spacers to join the bowls together, we will make relatively large capsules that will have potential to form switchable free-radical products as before. Now, the radical centres we make will have potential to jump between the halves of the capsule, as well as migrating around the two individual bowls, which might lead to even more complicated spectroscopic and switching behaviour. We will also study another new class of capsule, which have a rather different potential use. These will be the smallest covalent capsule molecules yet known, which will be of appropriate size to bind gas molecules like hydrogen, oxygen or carbon dioxide (among others). Supramolecular complexes of gases are very unusual. As well as their strong academic interest, complexation has the effect of making the gas more soluble than it would otherwise be. This has implications for two particular technological problems. First is waste remediation. A capsule that can bind CO2 strongly could strip that greenhouse gas from power station emissions for example. Second is in medicine, where particular isotopes of xenon and carbon dioxide can be used to add contrast to diagnostic images. An additive that can increase the concentration of those gases in bodily tissue will lead to clearer pictures.Dr Halcrow has strong expertise in the study of switchable materials based on metal-organic molecular compounds, while Dr Hardie is a world leader in the synthesis and host:guest chemistry of CTV and its analogues.

环三藜芦烯（“CTV”）是具有浅碗形状的刚性环状分子，其具有在其空腔中结合其他分子的良好能力。虽然可以容纳溶剂和其他小有机分子，但CTV特别值得注意的是它能够结合富勒烯（C60）和其他球形或球状化合物。因此，CTV是一类重要的超分子主体（称为空穴）的原型例子;即具有客人可进入的空腔的分子。该提案的标题化合物环三愈创木环烯（CTC）是CTV的一个略微缩小的版本，具有相同的刚性碗形状。该提案涉及将CTV化学扩展到几个新领域。首先，是通过制备具有可氧化官能团的CTV的化学改性衍生物，以这样的方式布置，使得在分子碗的边缘周围结合金属离子。先例表明，在这些条件下，碗状空腔可能很容易被氧化，产生金属稳定的自由基产物。人们特别感兴趣的是确定激进的中心是否能在碗里跳来跳去。如果可以，这将使化合物强烈吸收红外辐射。如果是这样的话，下一步将是研究打开和关闭红外吸收的方法。这可能是通过电化学或适当设计的材料，通过加热或冷却来实现的。像这样的可切换近红外吸收器在光纤通信设备中非常有用。将金属中心绑定到CTV的外围还将具有显著扩展其空腔的效果，使其直径增加一倍以上。我们还将研究这些新的扩大的洞穴作为小型和大型有机客人的宿主。特别感兴趣的是，在前一段中提到的光吸收和开关现象的腔中客体结合的影响。我们还将连接两个CTV碗，在彼此的顶部，以制造新的胶囊分子。我们将寻求两种方法来做到这一点。如果我们使用金属离子间隔物将碗连接在一起，我们将制造相对较大的胶囊，这些胶囊将有可能像以前一样形成可转换的自由基产物。现在，我们制造的激进中心将有可能在胶囊的两半之间跳跃，以及在两个单独的碗周围迁移，这可能导致更复杂的光谱和开关行为。我们还将研究另一类新的胶囊，它们具有相当不同的潜在用途。这些将是迄今已知的最小的共价胶囊分子，其大小将适合结合气体分子，如氢气，氧气或二氧化碳（以及其他）。气体的超分子复合物是非常罕见的。除了他们强烈的学术兴趣外，络合作用还具有使气体比其他情况下更易溶解的效果。这对两个特定的技术问题有影响。第一，废物治理。例如，一种能够强烈结合二氧化碳的胶囊可以从发电站排放的温室气体中分离出来。其次是在医学上，氙和二氧化碳的特定同位素可以用来增加诊断图像的对比度。Halcrow博士在研究基于金属有机分子化合物的可转换材料方面拥有丰富的专业知识，而Hardie博士在CTV及其类似物的合成和主客体化学方面处于世界领先地位。

项目成果

Hexasulfanyl analogues of cyclotriveratrylene

环三藜三烯的六硫基类似物

• DOI: 10.1016/j.tetlet.2014.03.025
• 发表时间: 2014
• 期刊: Tetrahedron Letters
• 影响因子: 1.8
• 作者: Little M

Stable mixed-valent radicals from platinum(II) complexes of a bis(dioxolene) ligand.

• DOI: 10.1002/chem.201304848
• 发表时间: 2014-05-19
• 期刊: CHEMISTRY-A EUROPEAN JOURNAL
• 影响因子: 4.3
• 作者: Loughrey, Jonathan J.;Sproules, Stephen;McInnes, Eric J. L.;Hardie, Michaele J.;Halcrow, Malcolm A.
• 通讯作者: Halcrow, Malcolm A.

Synthesis and electronic structures of new bis- and tris-_dioxolene complexes, and their delocalized mixed-_valent redox products

新型双和三二氧杂环戊烯配合物的合成和电子结构及其离域混合价氧化还原产物

• 作者: Jonathan J. Loughrey (Co-Author)

Platinum(ii) complexes of mixed-valent radicals derived from cyclotricatechylene, a macrocyclic tris-dioxolene.

• DOI: 10.1039/c5sc02776d
• 发表时间: 2015-12-01
• 期刊: Chemical science
• 影响因子: 8.4
• 作者: Loughrey JJ;Patmore NJ;Baldansuren A;Fielding AJ;McInnes EJL;Hardie MJ;Sproules S;Halcrow MA
• 通讯作者: Halcrow MA

Synthesis and methane-binding properties of disulfide-linked cryptophane-0.0.0.

• DOI: 10.1002/anie.201106512
• 发表时间: 2012-01
• 期刊: Angewandte Chemie
• 作者: M. A. Little;Jessica Donkin;J. Fisher;M. Halcrow;Jordan Loder;M. Hardie