Molecular design of novel luminescent complexes based on hybrid phosphine ligands for chemo- and biosensing applications

基于杂化膦配体的新型发光配合物的分子设计，用于化学和生物传感应用

• 批准号: 405832919
• 负责人: Professorin Dr. Evamarie Hey-Hawkins
• 金额: --
• 依托单位: Institut für Anorganische Chemie
• 依托单位国家: 德国
• 项目类别: Research Grants
• 财政年份: 2019
• 资助国家: 德国
• 起止时间: 2018-12-31 至 2022-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/405832919?language=en
• 关键词: Molecular; design; novel; luminescent; complexes

This joint project aims to provide access to novel luminescent systems based on a new class of multidonor hybrid phosphorus-containing heterocycles and their transition metal complexes for applications in chemo- and biosensing and bioimaging. The main synthetic efforts will be directed towards cyclic phosphine ligands containing two endocyclic phosphorus(III) atoms, two exocyclic chromophoric groups, and two tunable functions located on the endocyclic nitrogen atoms to allow maximal synthetic flexibility within a low-cost framework. These compounds will be synthesized by condensation reactions of primary heteroaryl phosphines with formaldehyde and subsequent ring formation through addition of primary amines or amino acids. Chromophoric heteroaromatic substituents at phosphorus and nitrogen provide luminescence properties and additional binding sites for supramolecular assemblies. Differing substituents on the endocyclic nitrogen atoms will also be used to modify the steric and electronic properties of the donor centers, and will simultaneously provide the means to fine-tune physical properties such as ligand lipo- and hydrophilicity and luminescence. The optical properties of metal complexes depend on the type of chromophore and metal ion. A variety of luminescence parameters will be achieved by employing d6, d8, and d10 metal ions (Ir(III), Pt(II), Au(I) und Cu(I)) with different coordination numbers and coordination spheres. For effective charge transfer and high luminescence, chromophoric groups should be coordinated to the metal center or be located in near proximity. Moreover, a number of chromophoric coligands will be coordinated at the metal center to modify the photophysical properties of the complexes. The unique structure of the targeted complexes will provide a basis for their substrate-induced luminescence response, which in turn results from redox transformations or host–guest complex formation. Quantum chemical investigations of the electronic structure will be performed for the synthesized complexes with the aim of revealing the orbitals involved in the transitions responsible for electronic absorption and luminescence. On the basis of an understanding of the spectroscopic origin and their structure–property relationships, the potential for the development of luminescent metal complexes for a variety of functions and applications, especially in the field of bioimaging and biosensing, will be evaluated. As insolubility of the complexes in water might restrict their suitability for bioimaging and biosensing, these complexes will also be converted to water-soluble hydrophilic nanoparticles for these studies.

该联合项目旨在提供基于一类新的多供体杂合含磷杂环及其过渡金属络合物的新型发光系统，用于化学和生物传感以及生物成像。主要的合成努力将针对环状膦配体含有两个内环磷（III）原子，两个环外发色团，和两个可调功能位于内环氮原子，以允许最大的合成灵活性内的低成本框架。这些化合物将通过伯杂芳基膦与甲醛的缩合反应和随后通过加成伯胺或氨基酸形成环来合成。在磷和氮上的发色杂芳族取代基为超分子组装提供发光性质和额外的结合位点。内环氮原子上的不同取代基也将用于改变供体中心的空间和电子性质，并且将同时提供微调物理性质如配体脂溶性和亲水性以及发光的手段。金属配合物的光学性质取决于发色团和金属离子的类型。通过采用具有不同配位数和配位球的d 6、d8和d10金属离子（Ir（III）、Pt（II）、Au（I）和Cu（I）），将实现各种发光参数。为了有效的电荷转移和高发光，发色团应与金属中心配位或位于附近。此外，许多发色团的共配体将在金属中心配位以改变配合物的物理化学性质。靶向复合物的独特结构将为其底物诱导的发光响应提供基础，这反过来又是氧化还原转化或主客体复合物形成的结果。将对合成的复合物进行电子结构的量子化学研究，目的是揭示负责电子吸收和发光的跃迁所涉及的轨道。在理解光谱起源及其结构-性质关系的基础上，将评估用于各种功能和应用的发光金属络合物的发展潜力，特别是在生物成像和生物传感领域。由于复合物在水中的不溶性可能限制其用于生物成像和生物传感的适用性，因此这些复合物也将被转化为水溶性亲水性纳米颗粒用于这些研究。