Corkett Alex J, Chen Zheng, Bogdanovski Dimitri, Slabon Adam, Dronskowski Richard
Chair of Solid-State and Quantum Chemistry, Institute of Inorganic Chemistry , RWTH Aachen University , 52056 Aachen , Germany.
Department of Materials and Environmental Chemistry , Stockholm University , Svante Arrhenius väg 16 C , 106 91 Stockholm , Sweden.
Inorg Chem. 2019 May 6;58(9):6467-6473. doi: 10.1021/acs.inorgchem.9b00670. Epub 2019 Apr 16.
Layered bismuth oxides exhibit a broad range of tunable physical properties as a result of their excellent structural versatility which facilitates compositional substitutions at both cationic and anionic positions. Here we expand this family in a new direction through the preparation of the first example of a bismuth-containing oxide carbodiimide, BiONCN, which assumes an extended variant of the anti-ThCrSi structure-type adopted by BiO Ch ( Ch = Se or Te) oxide chalcogenides. Electronic structure calculations reveal the title compound to be an indirect band gap semiconductor with a band gap of approximately 1.4 eV, in good agreement with the measured value of 1.8 eV, and intermediate between that of structurally related BiOS (1.12 eV) and β-BiO (2.48 eV). Mott-Schottky experiments demonstrate BiONCN to be an n-type semiconductor with a conduction band edge position of -0.37 V vs reversible hydrogen electrode. This study highlights the pseudochalcogenide nature of the N═C═N carbodiimide anion, which may be substituted in place of oxide or chalcogenide anions in this and potentially other structural classes as an effective means of electronic tuning.
