Mangham Barry, Hanson-Heine Magnus W D, Davies E Stephen, Wriglesworth Alisdair, George Michael W, Lewis William, Kays Deborah L, McMaster Jonathan, Besley Nicholas A, Champness Neil R
School of Chemistry, University of Nottingham, University Park, NG7 2RD, UK.
Phys Chem Chem Phys. 2020 Feb 26;22(8):4429-4438. doi: 10.1039/c9cp06427c.
A strategy to create organic molecules with high degrees of radical spin multiplicity is reported in which molecular design is correlated with the behaviour of radical anions in a series of BODIPY dyads. Upon reduction of each BODIPY moiety radical anions are formed which are shown to have different spin multiplicities by electron paramagnetic resonance (EPR) spectroscopy and distinct profiles in their cyclic voltammograms and UV-visible spectra. The relationship between structure and multiplicity is demonstrated showing that the balance between singlet, biradical or triplet states in the dyads depends on relative orientation and connectivity of the BODIPY groups. The strategy is applied to the synthesis of a BODIPY triad which adopts an unusual quartet state upon reduction to its radical trianion.
报道了一种用于创建具有高自由基自旋多重性的有机分子的策略，其中分子设计与一系列BODIPY二元化合物中自由基阴离子的行为相关。在每个BODIPY部分还原后会形成自由基阴离子，通过电子顺磁共振（EPR）光谱显示其具有不同的自旋多重性，并且在其循环伏安图和紫外可见光谱中具有独特的特征。证明了结构与多重性之间的关系，表明二元化合物中单重态、双自由基态或三重态之间的平衡取决于BODIPY基团的相对取向和连接性。该策略应用于BODIPY三元化合物的合成，该三元化合物在还原为其三价自由基阴离子时呈现出不寻常的四重态。
