A Luminescent Heterometallic Dirhodium−Silver Chain

A novel one-dimensional (1D) heterometallic chain, {[Rh2(dfpma)2(MeCN)4]2[Ag(MeCN)4]}[PF6]5 (1), is afforded from the in situ reaction of [ClRh(cod)]2 with [Ag(MeCN)4][PF6] and dfpma (dfpma = bis(difluorophosphine)methylamine). Dichroic crystals, which are obtained from MeCN/Et2O solutions, crystallize in the monoclinic space group C2/m with a = 13.570(5) Å, b = 20.895(9) Å, c = 13.810(6) Å, β = 104.904(7)°, V = 3784(3) Å3, Z = 4. X-ray diffraction studies reveal an asymmetric unit comprising two RhI2 dimers and a square planar AgI cation; this subunit propagates to form a 1D heterometallic chain. Compound 1 displays novel spectroscopic properties in the solid state, including temperature-dependent luminescence.