| Abstract: | Magnetoresponsive three‐membered rings of d‐ and f‐block elements have been thoroughly investigated with the help of electronic structure calculation methods. The magnetic response of the clusters was evaluated by the Nucleus Independent Chemical Shifts (NICS)zz‐scan curves, which in conjunction with symmetry‐based selection rules for the most significant translationally and rotationally allowed transitions helped rationalize and predict the orbital‐type of aromaticity/antiaromaticity of the clusters. The magnetoresponsive early (Groups 3, 4, and 5) transition metal M3 rings exhibit successive aromatic and antiaromatic zones separated by a nodal plane. The magnetoresponsive late (Groups 11 and 12) transition metal M3 rings exhibit long‐range aromatic zone with the NICSzz(R) values decaying rapidly and monotonically with respect to R. The magnetic response of Group 10 transition metal M3 rings is similar to that of the early transition metal M3 rings, but it is long‐range antiaromatic only for the c‐Ni3] cluster. The NICSzz‐scan curve of the (HtLa)3(μ2‐H)6] cluster is indicative of weak pure σ‐aromaticity due to the induced diatropic ring current from the translationally allowed a → e′ and e′ → a transitions. The aromatic–antiaromatic behavior of the (HtCe)3(μ2‐H)6]+ and (HtTm)3(μ2‐H)6]2− clusters is similar to that of the early d‐block elements. The magnetic response of (HtYb)3(μ2‐H)6]3− is similar to that of c‐Hg3]2−. The (HtLu)3(μ2‐H)6] cluster can be considered as a doubly (σ + π) aromatic system, with the σ‐aromatic component being much stronger than the π‐aromatic one. Finally, the (XtRe)3(μ2‐X)6] and (XtRu)3(μ2‐X)6]+ (X = Cl, Br, I) clusters exhibit significant aromatic character with the greatest contribution to the induced diatropic ring currents coming from π‐type transitions. © 2009 Wiley Periodicals, Inc. J Comput Chem 2010 |
