Department of Chemistry and Biochemistry , University of California , Santa Barbara , California 93106 , United States.
ChemMatCARS , University of Chicago , Argonne , Illinois 60493 , United States.
J Am Chem Soc. 2019 Feb 13;141(6):2604-2613. doi: 10.1021/jacs.8b12899. Epub 2019 Feb 4.
The synthesis and characterization of a new phthalocyanine (Pc) Mn-nitride complex, (Pc)MnN (2; Pc = 1,4,8,11,15,18,22,25-octaethoxy-Pc), as well as its stable, readily accessible oxidized (2 and 2) and reduced (2, 2) congeners is reported. This unique isostructural series displays switchable aromatic character spanning the aromatic (2), nonaromatic (2), and antiaromatic (2) triad, in addition to the open-shell radical states (2, 2). All complexes were structurally characterized and displayed significant structural distortions at the redox extrema (2, 2) consistent with proposed [16 or 18]annulene π ring circuit models. Spectroscopic and computational studies further support these models. This isolated, fully characterized, isostructural series spanning five redox states (2, 2, 2, 2, 2) is unique in both the Pc and related macrocyclic (ex. porphyrinoids) literature and may offer direct insight into structural-electronic correlations driven by switchable aromaticity.
报道了一种新型酞菁（Pc）锰氮配合物（Pc）MnN（2；Pc=1,4,8,11,15,18,22,25-辛氧基-Pc）的合成与表征，以及其稳定、易制备的氧化态（2和2）和还原态（2,2）同系物。该独特的同结构系列具有可切换的芳香性，跨越芳香族（2）、非芳香族（2）和反芳香族（2）三联体，以及开壳自由基态（2,2）。所有配合物均进行了结构表征，并在氧化还原极值（2,2）处显示出显著的结构畸变，与提出的[16 或 18]轮烯π 环电路模型一致。光谱和计算研究进一步支持这些模型。这个孤立的、完全表征的、具有五个氧化还原态（2,2,2,2,2）的同结构系列在 Pc 和相关大环（例如卟啉类）文献中都是独特的，可能为可切换芳香性驱动的结构-电子相关性提供直接的见解。
