Abstract
AbstractA 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.
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