Self‐Alignment of Low‐Valent Octanuclear Palladium Atoms |
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| Authors: | Kanako Nakamae Dr Yukie Takemura Dr Bunsho Kure Prof Takayuki Nakajima Prof Yasutaka Kitagawa Prof Tomoaki Tanase |
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| Institution: | 1. Department of Chemistry, Faculty of Science, Nara Women's University, Kitauoya‐nishi‐machi, Nara, 630‐8506 (Japan);2. Department of Materials Engineering Science, Graduate School of Engineering Science, Osaka University, 1‐3 Machikaneyama, Toyonaka, Osaka 560‐8531 (Japan) |
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| Abstract: | 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. |
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| Keywords: | metal atom chains octanuclear complexes palladium self‐assembly tetraphosphines |
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