On the Road to a Termolecular Complex with Acetone: A Heterometallic Supramolecular Network {[Rh<sub>2</sub>(O<sub>2</sub>CCF<sub>3</sub>)<sub>4</sub>]·μ<sub>2</sub>-OCMe<sub>2</sub>·[Cu<sub>4</sub>(O<sub>2</sub>CCF<sub>3</sub>)<sub>4</sub>]}
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A novel heterometallic supramolecular network {[Rh2(O2CCF3)4]·μ2-OCMe2·[Cu4(O2CCF3)4]}2∞ has been prepared by codeposition of the volatile mono(acetone) adduct [Rh2(O2CCF3)4·η1-OCMe2]2 and copper(I) trifluoroacetate, [Cu4(O2CCF3)4]. The product is of interest from the viewpoints of gas-phase supramolecular synthesis and a rare bridging coordination mode of acetone. It has been fully characterized by IR and NMR spectroscopy, elemental analysis, and X-ray diffraction. An X-ray structure revealed a layered 2D arrangement of the heterometallic {[Rh2(O2CCF3)4]·μ2-OCMe2·[Cu4(O2CCF3)4]} units built by axial intermolecular interactions of the open electrophilic Rh(II) and Cu(I) centers and O-atoms of neighboring carboxylate groups. The coordination of the acetone molecules within the {[Rh2(O2CCF3)4]·μ2-OCMe2·[Cu4(O2CCF3)4]} unit is asymmetric with the Rh−O and Cu−O distances being 2.2173(15) and 2.7197(17) Å, respectively. This work shows the potential of gas-phase deposition that may provide additional possibilities in supramolecular synthesis by utilizing intermolecular interactions and coordination bonds in a new way compared with conventional solution chemistry.
