Strong anisotropy barriers of two theoretically modeled cyano-bridged magnets [(PY5Me2)4M4Re(CN)7]5+ (M = VII, NiII): DFT predictions

On the basis of the experimentally synthesized [(PY5Me2)4Mn4Re(CN)7]5+, the theoretically modeled clusters of [(PY5Me2)4V4Re(CN)7]5+ and [(PY5Me2)4Ni4Re(CN)7]5+ both have strong magnetic anisotropy energy barriers.

Graphical abstractTwo theoretically modeled clusters of [(PY5Me2)4V4Re(CN)7]5+ and [(PY5Me2)4Ni4Re(CN)7]5+ both have strong magnetic anisotropy energy barriers on the basis of the experimentally synthesized [(PY5Me2)4Mn4Re(CN)7]5+.Figure optionsDownload full-size imageDownload as PowerPoint slideHighlights► The couplings of Mn4Re and V4Re are antiferromagnetic and that of Ni4Re is ferromagnetic. ► Two modeled cyano-bridged magnets V4Re and Ni4Re both have strong anisotropy barriers. ► The more closely orthogonal hard axes may be responsible for the larger negative D values of the optimized V4Re and Ni4Re. ► The largest local D and the most closely orthogonal hard axes of [PY5Me2Ni(CN)]+ are responsible for the largest D of the optimized Ni4Re. ► The larger Mn–N≡C angle is responsible for the larger calculated D value of the optimized Mn4Re.