Solvent Effects on the Assembly of [Cu2I2]- or [Cu4I4]-Based Coordination Polymers: Isolation, Structures, and Luminescent Properties
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Abstract
Four [Cu2I2]- or [Cu4I4]-based coordination polymers, [CuI(bpp)]n (1), {[Cu3I3(bpp)3]·2aniline·MeCN}n (2), {[Cu2I2(bpp)2]·2aniline}n (3), and [Cu4I4(bpp)2]n (4), were prepared by solvothermal reactions of CuI or Cu2(OH)2CO3 with 1,3-bis(4-pyridyl)propane (bpp) in different solvent systems. The preparation of 2 or 3 is involved in the in situ formation of aniline molecules and the reduction of Cu(II) to Cu(I). These compounds were characterized by elemental analysis, IR, and single crystal X-ray diffraction. Compound 1 consists of [Cu2I2] dimeric cores that link the neighboring ones via bpp bridges to form a one-dimensional double-bridged polymeric chain. Compound 2 or 3 has a similar chain structure in which the shape and size of the [Cu2I2(bpp)2]2 cavities that are occupied by MeCN/aniline or aniline solvent molecules are different from those of 1. Compound 4 has an intriguing two-dimensional 4-fold interpenetrated network in which each cubanelike [Cu4I4] core acts as a rare “seesaw”-shaped four-connecting node to interconnect four other equivalent ones via bpp bridges. The results did provide interesting insights into solvent effects on the construction of cluster-based coordination polymers. In addition, the photoluminescent properties of 1−4 in the solid state at ambient temperature were also investigated.
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