Abstract
Three copper(I) complexes, [Cu8I8(PMS)4(MeCN)2] n (1), Cu4I4(PMS)4 (2), and Cu2I2(PMS)4 (3) were prepared by the self‐assembly reaction of mole ratio‐controlled CuI and pentamethylene sulfide (PMS). Single crystal X‐ray diffraction analyses displayed crystal structures of three complexes based on new S‐shaped Cu8I8, cubane Cu4I4, and rhomboid Cu2I2 cluster units for 1–3, respectively. Crystal transformations between 1, 2, and 3 were controlled by the addition of PMS or CuI/acetonitrile. Luminescence properties of 1 and 2 were investigated. Complex 1 showed two very weak emission bands, which were assigned to HE band for λmax = 415 nm and LE band for λmax = 575 nm under ultraviolet irradiation (λex = 355 nm). Complex 2 displayed luminescence thermochromism with a slightly hypsochromic shift from 572 to 565 nm (λex = 355 nm).
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