Henan Key Laboratory of Crystalline Molecular Functional Materials, Henan International Joint Laboratory of Tumor Theranostical Cluster Materials, Green Catalysis Center, and College of Chemistry, Zhengzhou University, Zhengzhou 450001, China.
Key Laboratory of Material Chemistry for Energy Conversion and Storage, Ministry of Education, School of Chemistry and Chemical Engineering, Huazhong University of Science and Technology, Wuhan 430074, China.
J Am Chem Soc. 2022 Mar 30;144(12):5389-5399. doi: 10.1021/jacs.1c12767. Epub 2022 Mar 18.
Artificial systems for sequential chirality transmission/amplification and energy relay are perpetual topics that entail learning from nature. However, engineering chiral light-harvesting supramolecular systems remains a challenge. Here, we developed new chiral light-harvesting systems with a sequential Förster resonance energy transfer process where a designed blue-violet-emitting BINOL (1,1'-Bi-2-naphthol) compound, BINOL-di-octadecylamide (BDA), functions as an initiator of chirality and light absorbance, a new green-emitting hexagonal tetraphenylethene-based macrocycle (TPEM) with aggregation-induced emission serves as a conveyor, and Nile red (NiR) or/and a near-infrared dye, tetraphenylethene (TPE)-based benzoselenodiazole (TPESe), are the terminal acceptors. Benefiting from the close contact and large optical overlap between donors and acceptors at each level, triad and tetrad relaying systems sequentially and efficiently furnish chirality transmission/amplification and energy transfer along the cascaded line BDA-TPEM-NiR (or/and TPESe), leading to bright customized-color circularly polarized luminescence (CPL) and bright white-light-emitting CPL (CIE coordinates: 0.33, 0.34) with an amplified dissymmetry factor () of 3.5 × 10 over a wide wavelength range. This work provides a new direction for the construction of chiral light-harvesting systems for a broad range of applications in chiroptical physics and chemistry.
人工序列手性传递/放大和能量中继系统是从自然界中学习的永恒主题。然而，工程手性光捕获超分子系统仍然是一个挑战。在这里，我们开发了具有顺序Förster 共振能量转移过程的新型手性光捕获系统，其中设计的蓝紫色发射 BINOL（1,1'-双-2-萘酚）化合物 BINOL-二十八酰胺（BDA）作为手性和光吸收的引发剂，新型绿色发射六方四苯乙烯基大环（TPEM）具有聚集诱导发射作为输送器，尼罗红（NiR）或/和近红外染料，四苯乙烯（TPE）基苯并硒二唑（TPESe）是末端受体。得益于每个水平上供体和受体之间的紧密接触和大光学重叠，三联体和四联体中继系统沿级联线 BDA-TPEM-NiR（或/和 TPESe）顺序且有效地提供手性传递/放大和能量转移，从而导致定制颜色圆偏振发光（CPL）和明亮的白色 CPL（CIE 坐标：0.33,0.34），在很宽的波长范围内，放大的不对称因子（）为 3.5×10。这项工作为构建广泛应用于手征光物理和化学的手性光捕获系统提供了新的方向。
