4.8 Article

Photoinduced single-crystal-to-single-crystal phase transition and photosalient effect of a gold(I) isocyanide complex with shortening of intermolecular aurophilic bonds

Journal

CHEMICAL SCIENCE
Volume 6, Issue 2, Pages 1491-1497

Publisher

ROYAL SOC CHEMISTRY
DOI: 10.1039/c4sc02676d

Keywords

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Funding

  1. Funding Program for Next Generation World-Leading Researchers (NEXT) from the Japan Society for the Promotion of Science (JSPS) [G002]
  2. MEXT (Japan)
  3. JSPS KAKENHI [26810042]
  4. Grants-in-Aid for Scientific Research [26620053, 26810042] Funding Source: KAKEN

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We report the first photoinduced single-crystal-to-single-crystal (SCSC) phase transition of a gold complex that involves the shortening of intermolecular aurophilic bonds. This is also the first solid state photochromism of a gold complex. Upon UV irradiation, the blue-emitting crystals of the gold(I) isocyanide complex 1 (1B) transform into the weakly yellow-emitting polymorph 1Y. X-ray diffraction analyses reveal that this phase transition proceeds in an SCSC manner. After phase transition from 1B to 1Y, the intermolecular Au...Au separation decreases from 3.5041(14) to 3.2955(6) angstrom, resulting in a red-shifted emission. The photoinduced shortening of the aurophilic bond in the excited state initiates the change in the crystal structure from 1B to 1Y. Moreover, the crystal 1B showed a photosalient effect: the 1B crystals jump upon irradiation with strong UV light owing to the phase transition into 1Y. The aurophilic bond formation in the crystal generates the mechanical movement of the crystal.

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