Probing the structural origins of vapochromism of a triarylboron-functionalized platinum(II) acetylide by optical and multinuclear solid-state NMR spectroscopy |
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Authors: | Hudson Zachary M Sun Christina Harris Kristopher J Lucier Bryan E G Schurko Robert W Wang Suning |
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Institution: | Department of Chemistry, Queen's University, 90 Bader Lane, Kingston, Ontario, Canada K7L 3N6. |
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Abstract: | A vapoluminescent triarylboron-functionalized platinum(II) complex that displays a mechanism of vapochromism differing from all previously reported platinum(II) compounds has been synthesized. The luminescence color of 1 switches in response to many volatile organic compounds in the solid state, including hexanes, CH(2)Cl(2), benzene, and methanol. While vapochromism due to changes in Pt-Pt or π-π stacking interactions has been commonly observed, absorption and luminescence studies and single-crystal and powder X-ray diffraction data as well as multinuclear solid-state NMR experiments ((195)Pt, (13)C, (11)B, (2)H, and (1)H) revealed that the vapochromic response of 1 is instead due to changes in the excited-state energy levels resulting from local interactions of solvent molecules with the complex. Furthermore, these interactions result in inversion of the lowest-energy excited states of the complex in some cases, the first observation of this phenomenon in the solid state. |
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