Redox Switchable Photonic Materials Based on Organoimido-Polyoxometalate/Cyclodextrin Host-Guest Complexes

基于有机亚氨基多金属氧酸盐/环糊精主客体复合物的氧化还原可切换光子材料

• 批准号: EP/R042675/1
• 负责人: John Fielden
• 金额: $ 44.49万
• 依托单位: University of East Anglia
• 依托单位国家: 英国
• 项目类别: Research Grant
• 财政年份: 2018
• 资助国家: 英国
• 起止时间: 2018 至 无数据
• 项目状态: 已结题
• 来源: https://gtr.ukri.org/projects?ref=EP%2FR042675%2F1
• 关键词: Redox; Switchable; Photonic; Materials; Based

Photonic materials interact with light in useful and interesting ways. They enable its manipulation, and conversion into other forms of energy. One important class of photonic materials are non-linear optical (NLO) materials, which can be used to manipulate and adjust the properties of laser light beams. For example, they are used to make green lasers by second harmonic generation (SHG) from an infra-red source, and in electro-optic (EO) modulators that transfer digital electronic signals into fibre-optic telecommunications. At present, most commercial NLO materials are simple inorganic salts. These are inexpensive, durable and ideal for simple SHG applications. However, in telecommunications and computing they suffer from slow speed, as their responses originate from displacement of (relatively heavy) ions in response to the electric field of light. Molecular organic and metal-organic materials promise faster responses, because they arise from displacement of lighter, faster electrons, and also rational property tuning and the possibility of rapid property switching (i.e. on/off for optical or electrooptical transistors). But it is difficult to obtain molecules combining high NLO activity with adequate transparency and photostability, and adding the ability to reversibly switch between on/off states is a still greater challenge. Recently, we discovered a promising new class of molecular NLO materials based on polyoxometalates (POMs) - a type of molecular metal oxide cluster - connected to organic groups. These POM-based chromophores (POMophores) obtain high NLO coefficients from materials with small, stable organic groups and excellent transparency, and show redox properties that could be used to switch the NLO response.The next stage, addressed in this project, is to assemble POMophores into bulk materials that can be used in devices - specifically EO modulators and transistors. To do this, we must find a way to align all of the POMophores so that they point in the same direction and give a net NLO effect. This is challenging, as methods for controlled assembly of POM-based materials are currently very limited, and to achieve the goal we will develop a new approach where we first trap the POMophore in a molecular container. The molecular containers are designed in such a way that they form a film where the desired molecular orientation is forced on the POMophore. In addition to organising the POMophores to give bulk NLO properties, the containers will also protect them from degradation when we investigate redox-switching of the NLO response.POMs offer many other properties beyond non-linear optics - for example many POM clusters are excellent catalysts or photocatalysts due to their ability to rapidly accept and transfer electrons, some have magnetic and/or luminescence properties introduced by incorporating suitable heterometals into the POM framework, and POMs have also demonstrated anti-viral activity. Therefore, we expect that other areas of chemistry and materials science will benefit from methods enabling their encapsulation and control over their positioning on the nanoscale. Possibilities could include selective catalysis, solar energy conversion, memory devices, and even targeting of biologically/medicinally active POM species for therapeutic interventions. This project will lay the groundwork necessary for such developments, as well as potentially producing the new, high performance bulk NLO materials needed for future telecommunications and computing.

光子材料以有用且有趣的方式与光相互作用。它们可以使其操纵，并转换为其他形式的能量。一类重要的光子材料是非线性光学（NLO）材料，可用于操纵和调整激光光束的性能。例如，它们用于从红外源以及将数字电子信号转移到纤维电信电信的电 - 光电（EO）调节器中，通过第二次谐波生成（SHG）制成绿色激光器。目前，大多数商业NLO材料都是简单的无机盐。这些是廉价，耐用且非常适合简单的SHG应用程序。但是，在电信和计算中，它们的响应源于（相对重）离子的响应响应光的电场，它们的响应源于速度缓慢。分子有机和金属有机材料有望更快地响应，因为它们是由较轻，更快的电子的位移以及合理的性质调整以及快速属性转换的可能性（即，对于光学或电流晶体管的开/关）。但是，很难获得将高NLO活性与足够的透明度和光稳定性相结合的分子，并且增加在开/关状态之间可逆切换的能力仍然是一个更大的挑战。最近，我们发现了一种有希望的新型分子NLO材料，该材料基于多氧盐（POM）（POM） - 一种连接到有机基团的分子金属氧化物簇。这些基于POM的发色团（Pomophores）从具有小的，稳定的有机基团和出色透明度的材料中获得了高NLO系数，并显示可用于切换NLO响应的氧化还原性能。该项目中的下一个阶段是为了将Pomophores组装到可以在设备中使用的块状材料 - 特定于EO EO模量 - 特定于EO模块和晶体管。为此，我们必须找到一种对齐所有pomomotors的方法，以便它们指向相同的方向并产生净NLO效应。这是具有挑战性的，因为目前，基于POM的材料的受控组装方法非常有限，并且为了实现目标，我们将开发一种新方法，我们首先将Pomomphore捕获到分子容器中。分子容器的设计方式使它们形成薄膜，其中强迫所需的分子方向在Pomophore上被迫。 In addition to organising the POMophores to give bulk NLO properties, the containers will also protect them from degradation when we investigate redox-switching of the NLO response.POMs offer many other properties beyond non-linear optics - for example many POM clusters are excellent catalysts or photocatalysts due to their ability to rapidly accept and transfer electrons, some have magnetic and/or luminescence properties introduced by incorporating suitable heterometals into the POM框架和POM也表现出抗病毒活性。因此，我们预计，其他化学和材料科学领域将受益于方法，从而使其对纳米级的定位进行封装和控制。可能性可能包括选择性催化，太阳能转化，记忆设备，甚至针对生物学/药物活性POM物种进行治疗干预措施。该项目将为此类发展带来基础，并可能生产出新的，高性能的NLO NLO材料，用于将来电信和计算。

项目成果

Electrochemically-Switched 2nd Order Non-Linear Optical Response in an Arylimido-Polyoxometalate with High Contrast and Cyclability.

• DOI: 10.1002/anie.202215537
• 发表时间: 2023-01-26
• 期刊: ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
• 影响因子: 16.6
• 作者: Hood, Bethany R. R.;de Coene, Yovan;Torre Do Vale Froes, Afonso V. V.;Jones, Claire F. F.;Beaujean, Pierre;Liegeois, Vincent;MacMillan, Fraser;Champagne, Benoit;Clays, Koen;Fielden, John
• 通讯作者: Fielden, John

Electrochemically-Switched 2nd Order Non-Linear Optical Response in an Arylimido-Polyoxometalate with High Contrast and Cyclability

具有高对比度和可循环性的芳基酰亚胺多金属氧酸盐中的电化学切换二阶非线性光学响应

• DOI: 10.1002/ange.202215537
• 发表时间: 2022
• 期刊: Angewandte Chemie
• 作者: Hood B