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Predicting Nitrogen‐Based Families of Compounds: Transition‐Metal Guanidinates T CN 3 ( T =V, Nb, Ta) and Ortho‐Nitrido Carbonates T′ 2 CN 4 ( T′ =Ti, Zr, Hf)
Author(s) -
Luo Dongbao,
Qiao Xianji,
Dronskowski Richard
Publication year - 2021
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.202011196
Subject(s) - chemistry , nitride , carbodiimide , covalent bond , carbon nitride , stoichiometry , diazo , hydrogen bond , crystallography , metal , nitrogen , transition metal , computational chemistry , inorganic chemistry , molecule , medicinal chemistry , polymer chemistry , catalysis , organic chemistry , layer (electronics) , photocatalysis
Due to its unsurpassed capability to engage in various sp hybridizations or orbital mixings, carbon may contribute in expanding solid‐state nitrogen chemistry by allowing for different complex anions, such as the known NCN 2− carbodiimide unit, the so far unknown CN 3 5− guanidinate anion, and the likewise unknown CN 4 8− ortho‐nitrido carbonate ( onc ) entity. Because the latter two complex anions have never been observed before, we have chemically designed them using first‐principles structural searches, and we here predict the first hydrogen‐free guanidinates T CN 3 ( T =V, Nb, Ta) and ortho‐nitrido carbonates T′ 2 CN 4 ( T′ =Ti, Zr, Hf) being mechanically stable at normal pressure; the latter should coexist as solid solutions with the stoichiometrically identical nitride carbodiimides and nitride guanidinates. We also suggest favorable exothermic reactions as useful signposts for eventual synthesis, and we trust that the decay of the novel compounds is unlikely due to presumably large kinetic activation barriers (C−N bond breaking) and quite substantial Madelung energies stabilizing the highly charged complex anions. While chemical‐bonding analysis reveals the novel CN 4 8− to be more covalent compared to NCN 2− and CN 3 5− within related compounds, further electronic‐structure data of onc phases hint at their physicochemical potential in terms of photoelectrochemical water splitting and nonlinear optics.