Harnessing Bismuth Coordination Chemistry to Achieve Bright, Long-Lived Organic Phosphorescence

A new bismuth(III)-organic compound, Hphen[Bi-2(HPDC)(2)(PDC)(2)(NO3)]center dot 4H(2)O (Bi-1; PDC = 2,6-pyridinedicarboxylate and phen = 1,10-phenanthroline), was synthesized, and the structure was determined by single-crystal X-ray diffraction. The compound was found to display bright-blue-green phosphorescence in the solid state under UV irradiation, with a luminescent lifetime of 1.776 ms at room temperature. The room temperature and low-temperature (77 K) emission spectra exhibited the vibronic structure characteristic of Hphen phosphorescence. Time-dependent density functional theory studies showed that the excitation pathway arises from an energy transfer from the dimeric structural unit to Hphen, with participation from a nine-coordinate Bi center. The triplet state of Hphen is believed to be stabilized via supramolecular interactions, which, when coupled with the heavy-atom effect induced by Bi, leads to the observed long-lived luminescence. The compound displayed a solid-state quantum yield of over 27%. To the best of our knowledge, this is the first such compound to exhibit phenanthrolinium phosphorescence with such long-lived, room temperature lifetimes in the solid state. To further elucidate the energy-transfer mechanism, Ln(3+) (Ln = Eu, Tb, Sm) ions were successfully doped into the parent compound, and the resulting materials exhibited dual emission from Hphen and Ln, promoting tunability of the emission color.

Automated summary

A new bismuth(III)-organic compound was synthesized, displaying long-lived bright-blue-green phosphorescence in the solid state. This compound is the first to exhibit such long-lived phenanthrolinium phosphorescence at room temperature. Studies on the excitation pathway and energy transfer mechanism, as well as successful ion doping, allowed for tunability of the emission color.