The synthesis and structural analysis (single crystal X-ray data) of two mononuclear ([Cu(L-1)(CN)BF4 and [Cu(L-3)(CN)](BF4)) and three related, cyanide-bridged homodinuclear complexes ([{Cu(L-1)}(2)(CN)](BF4)(3)center dot 1.35 H2O, [{Cu(L-2)}(2)(CN))(BF4)(3) and [{Ni(L-3)}(2)(CN)](BF4)(3)) with a tetradentate (L-1) and two isomeric pentadentate bispidine ligands (L-2, L-3; bispidines are 3,7-diazabicyclo[3.3.1]nonane derivatives) are reported, together with experimental magnetic, electron paramagnetic resonance (EPR), and electronic spectroscopic data and a ligand-field-theory-based analysis. The temperature dependence of the magnetic susceptibilities and EPR transitions of the dicopper(II) complexes, together with the simulation of the EPR spectra of the mono-and dinuclear complexes leads to an anisotropic set of g- and A-values, zero-field splitting (ZFS) and magnetic exchange parameters (Cu1:g(z) = 2.055, g(x) = 2.096, g(y) = 2.260, A(z) = 8, A(x) = 8, A(y) = 195 x 10(-4) cm(-1), Cu2: g and A as for Cu-1 but rotated by the Euler angles alpha = -6 degrees, beta = 100 degrees, D-exc = -0.07 cm(-1), E-exc/D-exc = 0.205 for [{Cu(L-1)}(2)(CN)](BF4)(3)center dot 1.35 H2O; Cu1,2: g(z) = 2.025, g(x) = 2.096, g(y) = 2.240, A(z) = 8, A(x) = 8, A(y) = 190 x 10(-4) cm(-1), D-exc = -0.159 cm(-1), E-exc/D-exc = 0.080 for [{Cu(L-2)}(2)(CN)](BF4)(3)). Thorough ligand-field-theory-based analyses, involving all micro states and all relevant interactions (Jahn-Teller and spin-orbit coupling) and DFT calculations of the magnetic exchange leads to good agreement between the experimental observations and theoretical predictions. The direction of the symmetric magnetic anisotropy tensor D-exc in [{Cu(L-2)}(2)(CN)](BF4)(3) is close to the Cu center dot center dot center dot Cu vector (22 degrees), that is, nearly perpendicular to the Jahn-Teller axis of each of the two Cu-II centers, and this reflects the crystallographically observed geometry. Antisymmetric exchange in [{Cu(L-1)}(2)(CN)1(BF4)(3)center dot 1.35 H2O causes a mixing between the singlet ground state and the triplet excited state, and this also reflects the observed geometry with a rotation of the two Cu-II sites around the Cu center dot center dot center dot Cu axis.