Photolysis of red cis- and trans-[Cr^III(cyclam)(N₃)₂](ClO₄) (1a, 2a) (cyclam = 1,4,8,11-tetraazacyclotetradecane) in the solid state or aqueous solution by light affords the nitridochromium(V) complexes of cis- or trans-[Cr^V-(N)(cyclam)(N₃)](ClO₄) (3a) and dinuclear [{trans-[Cr^V(N)(cyclam)]}₂(μ-N₃)](ClO ₄)₃·3.5H₂O (4a), respectively. 4a was converted to the bis(tetraphenylborate)-azide-2C₂H₅OH salt (4b). Crystallization of 4a from acetonitrile-after addition of AgClO₄ and removal of AgN₃-yields octahedral trans-[Cr^V(N)(cyclam)(NCCH₃)](ClO₄)₂ (5a). The crystal structures of 1a, 2b (which is the tetraphenylborate salt of 2a), 4a,b, 5a,b have been determined by single-crystal X-ray crystallography. All nitridochromium(V) compounds contain the trans-[Cr^V(N)(cyclam)]²⁺ fragment with an N≡Cr^V moiety (1.56 ± 0.01 Å). The electronic spectra of d¹ configurated complexes display three low-intensity d-d bands which have been assigned in C_4v symmetry as (xy) ((xz,yz) ²B₂ → ²E, (xy) → (x² - y²) ²B₂ → ²B₁, and (xy) → (z²) ²B₂ → ²A₁, where the molecular z-axis coincides with the N≡Cr vector. Ligand-field parameters within the angular overlap model (AOM) of e_σ^cyclam = 7300-8600, e_σ^ax = 22 000, e_σ^ax = 21300-25000 cm^-1 have been determined which reproduce the experimental electronic spectra well. Temperature-dependent magnetic susceptibility measurements and X-band EPR spectroscopy on solid samples of 4a containing a linear Cr^V-N=N=N-Cr^V moiety revealed a weak intramolecular antiferromagnetic exchange coupling which is nearly absent in 4b containing a bent azido bridge. A mechanism for this unexpected coupling in 4a is proposed.