The structure and magnetic properties of the bimetallic borohydride-bridged dysprosocenium compound [{(η⁵-Cp^ttt)(η⁵-Cp^Me4t)Dy}₂(μ:κ²:κ²-BH₄)]⁺[B(C₆F₅)₄]^- ([3_Dy][B(C₆F₅)₄]) are reported along with the solution-phase dynamics of the isostructural yttrium and lutetium analogues (Cp^ttt is 1,2,4-tri(tert-butyl)cyclopentadienyl, Cp^Me4t is tetramethyl(tert-butyl)cyclopentadienyl). The synthesis of [3_M][B(C₆F₅)₄] was accomplished in the 2:1 stoichiometric reactions of [(η⁵-Cp^ttt)(η⁵-Cp^Me4t)Dy(BH₄)] (2_M) with [CPh₃][B(C₆F₅)₄], with the metallocenes 2_M obtained from reactions of the half-sandwich complexes [(η⁵-Cp^ttt)M(BH₄)₂(THF)] (1_M) (M = Y, Dy, Lu) with NaCp^Me4t. Crystallographic studies show significant lengthening of the M···B distance on moving through the series 1_M, 2_M, and 3_M, with essentially linear {M···B···M} bridges in 3_M. Multinuclear NMR spectroscopy indicates restricted rotation of the Cp^ttt ligands in 3_Y and 3_Lu in solution. The single-molecule magnet (SMM) properties of [3_M][B(C₆F₅)₄] are characterized by Raman and Orbach processes, with an effective barrier of 533(18) cm^-1 and relaxation via the second-excited Kramers doublet. Although quantum tunneling of the magnetization (QTM) was not observed for [3_M][B(C₆F₅)₄], it was, surprisingly, found in its magnetically dilute version, which has a very similar barrier of U_eff = 499(21) cm^-1. Consistent with this observation, slightly wider openings of the magnetic hysteresis loop at 2 K are found for [3_M][B(C₆F₅)₄] but not for the diluted analogue. The dynamic magnetic properties of the dysprosium SMMs and the role of exchange interactions in 3_Dy are interpreted with the aid of multireference ab initio calculations.

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