Tahaoglu, DuyguAlkan, FahriDurandurdu, Murat2021-12-152021-12-1520211610-29400948-5023PubMed ID34845522https //doi.org/10.1007/s00894-021-04980-1https://hdl.handle.net/20.500.12573/1074This work was supported by Research Fund of Abdullah Gul University (Project Number: FDK-2018-122).In this study, we provide a theoretical evaluation of relative stabilities and electronic structure for [BnXn](2-) clusters (n = 10, 12, 13, 14, 15, 16). Structural and electronic characteristics of [BnXn](2-) clusters are examined by comparison with the [B12X12](2-) counterparts with a focus on the substituent effects (X = H, F, Cl, Br, CN, BO, OH, NH2) on the electronic structure, electron detachment energies, formation enthalpies, and charge distributions. For the electronic structure and electron detachment energies, substituent effects on boron clusters are shown to follow a very similar trend to the mesomeric and inductive effects (+/- M and +/- I) of pi-conjugated systems, and the most stable derivatives in terms of HOMO/LUMO and electron detachment energies are calculated for CN and BO substituents due to strong -M effects. In the case of formation enthalpies for larger boron clusters (n >= 13), the icosahedral barrier is shown to increase with the halogen and CN substitution, whereas it is possible to reduce the icosahedral barrier for the cases of X = OH and NH2. It is shown that this reduction results from destabilizing the [B12X12](2-) cluster with electronic (+ M) and symmetry effects induced by OH and NH2 ligands.enginfo:eu-repo/semantics/closedAccessSubstitutionInductive effectMesomeric effectIcosahedral barrierBoron clustersarticleVolume 27 Issue 12