Temperature-controlled formation of olygomeric and polymeric compounds based on [Re4Te4(CN)12]4– cluster anions and Tm3+/1,10-phen complex cations

•Two new compounds based on [Re4Te4(CN)12]4−, Tm3+ and phen were obtained.•Temperature of crystallization process determines the degree of polymerization.•The mechanism of crystallization in EtOH/H2O media is discussed.•X-Ray diffraction, IR and thermal analysis studies were reported.

Self-assembly reaction of [Re4Te4(CN)12]4– tetrahedral rhenium chalcocyanide cluster anions, Tm3+ cations and 1,10-phenanthroline in an H2O/EtOH medium was investigated at different temperatures. Slow mixing of reagent solutions at the room temperature lead to formation of cluster compound (1) containing unique trimeric anionic fragment [{Tm(phen) (H2O)4}{Tm(phen)2(H2O)3}{Tm(phen)2(H2O)2}{Re4Te4(CN)12}3]3− (A1, phen = 1,10-phenanthroline). Oligomeric anion A1 shows an unusual U-shaped structure build from three cluster anions and three {Tm(phen)n(H2O)m}3+ (n = 1, 2; m = 2–4) complex cations linked to each other by CNTmNC covalent bonds and two couples of short OH…N hydrogen bonds. At the elevated (80–100 °C) temperatures the initial reaction products were dissolved, however, further increase of temperature up to 150 °C resulted in formation of layered (2D) coordination polymer K[{Tm(phen) (H2O)3}{Re4Te4(CN)12}]·0.5H2O (2). In addition to the experimental and X-Ray structural analysis data, thermal decomposition of compounds is also discussed.

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