Circularly polarized triplet exciton emission from chiral MOF-immobilized and -organized copper(I) complexes

激发态的手性光活性化合物是极大的兴趣，因为他们可以表现出圆偏振发光（CPL），尚未充分开发潜力的对映选择性传感器，数据存储，（3D-）OLED，或超快开关在量子密码学应用。目前大多数CPL化合物是基于荧光态和镧系元素，这两者都不是光电应用的最佳选择。然而，具有高量子产率和高辐射速率常数的磷光CPL材料的设计探索得少得多，因为形式上自旋禁戒的T1发射需要与具有足够电子跃迁偶极矩的Sn态耦合到基态，虽然它们中的每一个可以具有不同的磁跃迁偶极矩M取向因此，预测CP磷光或甚至CP-TADF的程度，（热激活延迟荧光）是困难的，并且已知的少数实例显示出相对弱的CPL。金属有机框架（MOF）是用于具有先进物理性能的新型材料的有针对性设计的有希望的平台，例如激光、多光子吸收和客体、温度或压力相关发光。将光活性分子发光体固定在刚性晶体配位网络中，可以显著提高其发光参数（发光寿命、量子产率等）由于增加的光稳定性、非辐射失活的抑制以及发光体在3D空间中的目标对准和布置。在这个合作项目中，我们的目标是将我们的专业知识联合收割机用于构建含有手性高效有机金属Cu（I）发光体的多孔MOF，这些发光体可以从它们的T1状态或通过TADF发射，排列在三维晶格中。为此，我们将遵循一个非常具体的设计策略，以获得有益的CPL性能的单晶，粉末和薄膜，并采用这些新材料的CP-PhOLED。

Excited states of chiral photoactive compounds are of great interest because they can exhibit circularly polarized luminescence (CPL) with a yet to fully explore potential in enantioselective sensors, data storage, (3D-)OLEDs, or ultrafast switching in quantum cryptographical applications. The majority of current CPL compounds is based on fluorescent states and lanthanides, both of which are not the optimal choice for optoelectronic applications. However, the design of phosphorescent CPL materials with high quantum yield and high radiative rate constants is much less explored as the formally spin-forbidden T1 emission requires coupling with Sn states of sufficient electronic transition dipole moment to the ground state, while each of them may have a different orientation of the magnetic transition dipole moment m (leading to partial cancellation of the overall m) that is necessary for strong CPL. Therefore, prediction of the extent of CP phosphorescence or even CP-TADF (thermally activated delayed fluorescence) is difficult, and the few examples known show relatively weak CPL.Metal-organic frameworks (MOFs) are promising platforms for the targeted design of novel materials with advanced photophysical properties, such as lasing, multi-photon absorption and guest, temperature or pressure dependent luminescence. The immobilization of photoactive molecular luminophores in a rigid crystalline coordination network can significantly improve their luminescence parameters (luminescence lifetime, quantum yield, etc.) due to increased photo-stability, a suppression of non-radiative deactivation as well as a targeted alignment and arrangement of the luminophores in 3D space. Within this collaborative project, we aim to combine our expertise for the construction of porous MOFs containing chiral highly-efficient organometallic Cu(I) luminophores, which can emit from their T1 state or via TADF, arranged in a three-dimensional lattice. For this, we will follow a very specific design strategy to obtain beneficial CPL properties in single crystals, powders and films, and employ these new materials in CP-PhOLEDs.