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带有螺旋供体-受体配体的铂配合物实现高达900纳米的双发光和红外圆偏振发光。

Dual luminescence and infrared circularly polarized luminescence up to 900 nm with platinum complexes bearing a helical donor-acceptor ligand.

作者信息

Vázquez-Domínguez Pablo, Horojat Maher, Suits Eva, José Fernández de Córdova Francisco, Vanthuyne Nicolas, Jacquemin Denis, Ros Abel, Favereau Ludovic

机构信息

Institute for Chemical Research (CSIC-US) C/Américo Vespucio 49 E-41092 Seville Spain

Department of Organic Chemistry, Innovation Centre in Advanced Chemistry, ORFEO-CINQA, University of Seville, C/Prof. García González 1 41012 Seville Spain.

出版信息

Mater Chem Front. 2024 Sep 6;8(22):3799-3806. doi: 10.1039/d4qm00632a. eCollection 2024 Nov 4.

Abstract

Chiral molecular materials able to emit circularly polarized luminescence (CPL) have attracted considerable interest in the last few decades, due to the potential of CP-light in a wide range of applications. While CP luminescent molecules with blue, green, and yellow emissions are now well-reported, NIR CPL from organic and organometallic compounds lags behind due to the dual challenge of promoting radiative deexcitation of the excited state in this low energy region while assuring a significant magnetic dipole transition moment, a prerequisite for generating CPL. Based on a versatile axially chiral arylisoquinoline ligand, we report the synthesis and chiroptical properties of chiral donor-acceptor platinum(ii) complexes displaying CPL that extends up to almost 900 nm. Interestingly, these emitters show both fluorescence and phosphorescence emissions in solution, with intensities depending on the charge-transfer character of the organic ligand. Experimental and theoretical investigations show that this feature strongly impacts the intersystem crossing event between the singlet and triplet excited states of these complexes and the related phosphorescence lifetime. The effect is less important regarding the CPL, and most complexes show luminescence dissymmetry factors with values up to 2 × 10 around 800 nm.

摘要

在过去几十年中,能够发射圆偏振光(CPL)的手性分子材料因其在广泛应用中的潜力而备受关注。虽然目前已对具有蓝色、绿色和黄色发射的CP发光分子进行了充分报道,但有机和有机金属化合物的近红外CPL由于在这个低能量区域促进激发态的辐射去激发以及确保显著的磁偶极跃迁矩(产生CPL的先决条件)这两个双重挑战而滞后。基于一种通用的轴向手性芳基异喹啉配体,我们报道了显示CPL且延伸至近900 nm的手性供体-受体铂(II)配合物的合成及手性光学性质。有趣的是,这些发光体在溶液中同时表现出荧光和磷光发射,其强度取决于有机配体的电荷转移特性。实验和理论研究表明,这一特性强烈影响这些配合物单重态和三重态激发态之间的系间窜越事件以及相关的磷光寿命。对于CPL而言,这种影响较小,并且大多数配合物在800 nm左右显示出高达2×10的发光不对称因子值。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/50ed/11423793/63fd0397f292/d4qm00632a-f1.jpg

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