A luminescent heterometallic dirhodium-silver chain

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