Four new Cu6S6 cluster-based coordination compounds: synthesis, crystal structures and fluorescence properties

Abstract

A hexagonal prismatic Cu₆S₆ cluster exhibits excellent near-infrared fluorescence properties due to its short Cu–Cu bonds, however, the construction of Cu₆S₆ cluster-based compounds with extended structures is still a challenge. Here, four new Cu₆S₆ cluster-based coordination compounds, formulated as Cu₃(pymt)₃ (1), {(CuCN)₂[Cu₃(mpymt)₃]}_n (2), {(CuSCN)[Cu₃(mpymt)₃]}_n (3) and {(CuCN)₂[Cu₃(dmpymt)₃]·CH₃CN}_n (4) (Hpymt = pyrimidine-2-thiolate, Hmpymt = 4-methyl-pyrimidine-2-thione and Hdmpymt = 4,6-dimethylpyrimidine-2-thione), have been synthesized through the reactions of mercaptopyrimidine derivatives and CuCN or CuSCN under solvo-thermal conditions and characterized by single-crystal X-ray diffraction, powder X-ray diffraction, IR spectroscopy, elemental analysis, and thermal gravimetric analysis. Single-crystal X-ray diffraction analysis reveals that compound 1 is a zero-dimensional Cu₆(pymt)₆ molecule containing a distorted pseudo-hexagonal prismatic Cu₆S₆ core. Compounds 2 and 4 with isomorphic frameworks but different organic linkers show a rare three-dimensional framework with nor topology constructed from Cu₆(mpymt)₆ units and one-dimensional chiral [Cu(CN)]_n chains; compared with compound 2, a more hydrophobic one-dimensional channel in compound 4 is observed due to the increase of the methyl groups on the pyrimidine ligand, in which acetonitrile molecules are filled in the channels of compound 4. Compound 3 shows a rare two-dimensional layer constructed from Cu₆(mpymt)₆ units and one-dimensional puckered (CuSCN)_n chains. For the first time, Cu₆S₆ clusters are connected to one-dimensional inorganic CuCN (or CuSCN) chains through mercaptopyrimidine derivatives to obtain extended arrays in compounds 2–4. The crystals of compounds 1–4 in the solid state all show apparent red light emission. Compound 4 shows sensitive luminescence quenching response to nitrobenzene (NB), and the corresponding quenching constant (K_sv) and detection limit are 2.06 × 10³ M⁻¹ and 9.27 ppm, respectively. This study provides a new strategy to construct Cu₆S₆ cluster-based coordination polymers that have great potential in various applications such as luminescence sensing.