Maiti Avijit, Sobottka Sebastian, Chandra Shubhadeep, Jana Debayan, Ravat Prince, Sarkar Biprajit, Jana Anukul
Tata Institute of Fundamental Research Hyderabad, Gopanpally, Hyderabad 500046, Telangana, India.
Institut für Chemie und Biochemie, Anorganische Chemie, Freie Universität Berlin, Fabeckstraße 34-36, 14195 Berlin, Germany.
J Org Chem. 2021 Dec 3;86(23):16464-16472. doi: 10.1021/acs.joc.1c01827. Epub 2021 Nov 15.
Herein, we report diamidocarbene (DAC)-based Thiele and Tschitschibabin hydrocarbons, diradicaloids that contain four carbonyl/amido functional groups. The impact of two different π-conjugated spacers, -phenylene vs ,'-biphenylene, has been realized. The quantum chemical calculations suggest diamidocarbene (DAC)-based Thiele hydrocarbon (-phenylene bridged) closed-shell singlet is the ground state, whereas for the diamidocarbene (DAC)-based Tschitschibabin hydrocarbon (,'-biphenylene bridged), open-shell singlet is the ground state. The influence of two different π-conjugated spacers also has been reflected in their UV-vis spectra. To gain more information on the diamidocarbene (DAC)-based Thiele and Tschitschibabin hydrocarbons, we have also carried out cyclic voltammetry investigations along with UV-vis-NIR-spectroelectrochemical studies of their corresponding 2-e oxidized product.
在此，我们报道了基于二氨基卡宾（DAC）的蒂勒烃和契奇巴宾烃，它们是含有四个羰基/酰胺基官能团的双自由基类化合物。已经认识到两种不同的π共轭间隔基，即亚苯基对亚联苯基的影响。量子化学计算表明，基于二氨基卡宾（DAC）的蒂勒烃（亚苯基桥连）的闭壳单重态是基态，而基于二氨基卡宾（DAC）的契奇巴宾烃（亚联苯基桥连）的开壳单重态是基态。两种不同的π共轭间隔基的影响也反映在它们的紫外-可见光谱中。为了获得更多关于基于二氨基卡宾（DAC）的蒂勒烃和契奇巴宾烃的信息，我们还进行了循环伏安法研究以及对其相应的2-电子氧化产物的紫外-可见-近红外光谱电化学研究。
