Six Mo(iv)-Cu(ii) complexes, [Cu(tpa)]2[Mo(CN) 8]·15H2O (1, tpa = tris(2-pyridylmethyl)amine), [Cu(tren)]2[Mo(CN)8]·5.25H2O (2, tren = tris(2-aminoethyl)amine), [Cu(en)2][Cu0.5(en)][Cu 0.5(en)(H2O)][Mo(CN)8]·4H2O (3, en = ethylenediamine), [Cu(bapa)]3[Mo(CN)8] 1.5·12.5H2O (4, bapa = bis(3-aminopropyl)amine), [Cu(bapen)]2[Mo(CN)8]·4H2O (5, bapen = N,N′-bis(3-aminopropyl)ethylenediamine), and [Cu(pn)2][Cu(pn)] [Mo(CN)8]·3.5H2O (6, pn = 1,3-diaminopropane), were synthesized and characterized. Single-crystal X-ray diffraction analyses show that 1-6 have different structures varying from trinuclear clusters (1-2), a one-dimensional belt (3), two-dimensional grids (4-5), to a three-dimensional structure (6). Magnetic and ESR measurements suggest that 1-6 exhibit thermally reversible photoresponsive properties on UV light irradiation through a Mo(iv)-to-Cu(ii) charge transfer mechanism. A trinuclear compound [Cu(ii)(tpa)]2[MoV(CN)8](ClO4) (7) was synthesized as a model of the photoinduced intermediate.
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