Maniappan Sonia, Reddy Kumbam Lingeshwar, Kumar Jatish
Department of Chemistry, Indian Institute of Science Education and Research (IISER) Tirupati Tirupati - 517507 India
Chem Sci. 2022 Nov 28;14(3):491-498. doi: 10.1039/d2sc05794h. eCollection 2023 Jan 18.
Since the observation of chirality at the nanoscale, research focused towards the design and synthesis of optically active nanomaterials has been at a brisk pace. In this regard, carbon based zero dimensional nanomaterials have attracted vast attention due to their rich optical properties, abundance of raw materials, minimal environmental hazardousness, good solubility, and ease of surface modification. However, efforts focused towards the synthesis of chiral carbon nanodots exhibiting optical activity both in their ground and excited states are rather scarce. Herein, we report a facile synthetic approach for the preparation of three sets of intrinsically chiral carbon nanodots that exhibit intense circularly polarized luminescence. Synthesis under optimized conditions using l- and d-isomers of the chiral precursors led to the formation of carbon nanodots that displayed mirror image circular dichroism and circularly polarized luminescence signals revealing their ground and excited state chirality. The experimental results are supportive of the reported core-shell model comprising an achiral carbon core that is enclosed within an amorphous shell contributing to the chiral luminescence. The luminescence anisotropy and wavelength could be tuned by varying the experimental conditions such as temperature and pH. The chiral emissive properties of the nanoparticles could be demonstrated in free-standing polymeric films revealing their potential to be used as chiral light emitting agents in optical devices, data storage and security tags. Being the first observation of intrinsic circularly polarized luminescence from a range of carbon nanodots, both in the solution and solid state, we envisage that the work will open new avenues for the investigation of excited stated chirality at the nanoscale.
自从在纳米尺度观察到手性以来,针对光学活性纳米材料的设计与合成的研究一直进展迅速。在这方面,碳基零维纳米材料因其丰富的光学性质、丰富的原材料、最小的环境危害性、良好的溶解性以及易于表面修饰而备受关注。然而,致力于合成在基态和激发态均表现出光学活性的手性碳纳米点的努力却相当稀少。在此,我们报道了一种简便的合成方法,用于制备三组表现出强烈圆偏振发光的本征手性碳纳米点。使用手性前体的 l - 和 d - 异构体在优化条件下进行合成,导致形成了显示镜像圆二色性和圆偏振发光信号的碳纳米点,揭示了它们的基态和激发态手性。实验结果支持所报道的核壳模型,该模型由一个非手性的碳核被包裹在一个对手性发光有贡献的无定形壳层内组成。发光各向异性和波长可以通过改变温度和 pH 等实验条件来调节。纳米颗粒的手性发射特性可以在独立的聚合物薄膜中得到证明,揭示了它们在光学器件、数据存储和安全标签中用作手性发光剂的潜力。作为首次在溶液和固态中对一系列碳纳米点的本征圆偏振发光的观察,我们设想这项工作将为纳米尺度激发态手性的研究开辟新的途径。