Self-alignment of low-valent octanuclear palladium atoms

A linear tetraphosphine, meso-bis[(diphenylphosphinomethyl)phenylphosphino]methane (dpmppm) was used to synthesize linear octapalladium-extended metal atom chains as discrete molecules of [Pd8(μ-dpmppm)4](BF4)4 (1) and [Pd8(μ-dpmppm)4L2](BF4)4 (L=2,6-xylyl isocyanide (XylNC; 2), acetonitrile (3), and N,N-dimethylformamide (dmf; 4)), which are stable in the solution states and show interesting temperature-dependent photochemical properties in the near IR region. Variable temperature NMR studies demonstrated that at higher temperature T≈140 °C the Pd8 chains were dissociated into Pd4 fragments, which were thermodynamically self-aligned to restore the Pd8 chains at lower temperature T<60 °C. The coldspray ionization mass spectra suggested a possibility for further aggregation of the linear tetrapalladium units.