The neutral and cationic dinuclear gold(I) compounds [(μ-N–N)(AuR)₂] (N–N = 2,2′-azobispyridine (2-abpy), 4,4′-azobispyridine (4-abpy); R = C₆F₅, C₆F₄OC₁₂H₂₅–p, C₆F₄OCH₂C₆H₄OC₁₂H₂₅–p) and [(μ-N–N){Au(PR₃)}₂](CF₃SO₃)₂ (N–N = 2-abpy, 4-abpy, R = Ph, Me) have been obtained by displacement of a weakly coordinated ligand by an azobispyridine ligand. The corresponding silver(I) dinuclear [(μ-2-abpy){Ag(CF₃SO₃)(PPh₃)}₂] and polynuclear [{Ag(CF₃SO₃)(4-abpy)}_n] compounds have been obtained. The molecular structures of [(μ-2-abpy){Au(PPh₃)}₂](CF₃SO₃)₂ and [(μ-4-abpy){Au(PMe₃)}₂](CF₃SO₃)₂ have been confirmed by X-ray diffraction studies and feature linear gold(I) centers coordinated by pyridyl groups, and non-coordinated azo groups. In contrast the X-ray structure of [(2-abpy){Ag(CF₃SO₃)(PPh₃)}₂] shows tetracoordinated silver(I) centers involving chelating N–N coordination by pyridyl and azo nitrogen atoms. The gold(I) compounds with a long alkoxy chain do not behave as liquid crystals, and decompose before their melting point. The soluble gold(I) derivatives are photosensitive in solution and isomerize to the cis azo isomer under UV irradiation, returning photochemically or thermally to the most stable initial trans isomer. The silver(I) derivative [(2-abpy){Ag(CF₃SO₃)(PPh₃)}₂] also photoisomerizes in solution under UV irradiation, showing that its solid state structure, which would block isomerization by azo coordination, is easily broken. These processes have been monitored by UV-vis absorption and ¹H NMR spectroscopy. All these compounds are non-emissive in the solid state, even at 77 K.