The persistent emission that remains after excitation light irradiation is stopped enables high-contrast imaging without relying on surrounding autofluorescence. However, the luminance of common persistent emitting materials hardly increases even when the excitation light intensity increases. Therefore, persistent emission has not been utilized for high-resolution imaging. Here we introduce approaches to obtain high-resolution afterglow information using persistent room temperature phosphorescence (RTP). In order to obtain the high-resolution afterglow information, it is necessary to improve the RTP yield and suppress the saturation of RTP brightness under strong light excitation. We explain the molecular designs to enhance the RTP yield using unique dynamic quantum chemical calculations. For the suppression of the RTP brightness with excitation irradiance, Forster resonance energy transfer to the accumulated triplet excitons in strong excitation is discussed. Finally, afterglow emission from the individual nanoparticles of materials showing bright persistent RTP was demonstrated in an atmospheric and aqueous solution environment.
Afterglow emission allows for imaging that is independent of autofluorescence under ambient conditions. Although higher-resolution afterglow is required for increasing the quality of the autofluorescence-free emission imaging, increasing the excitation intensity to generate brighter afterglow emission decreases the resolution of afterglow images. Therefore, methods and materials that provide afterglow imaging with higher resolution remain to be developed. In this study, we performed photoinduced triplet depletion and demonstrated improved resolution of bright afterglow emission using the depletion. Triplet depletion is related to charge separation via photoionization from a triplet state caused by the depletion and subsequent rapid singlet formation. Triplet excitons that accumulated in a solid material by excitation were depleted under irradiation using a depletion beam with a longer wavelength than the absorption wavelength of the material. A higher-resolution afterglow image with an improvement of 25% was obtained by simultaneously focusing a donut-shaped depletion beam and an excitation beam.
Afterglow emission allows for imaging that is independent of autofluorescence under ambient conditions. Although higher-resolution afterglow is required for increasing the quality of the autofluorescence-free emission imaging, increasing the excitation intensity to generate brighter afterglow emission decreases the resolution of afterglow images. Therefore, methods and materials that provide afterglow imaging with higher resolution remain to be developed. In this study, we performed photoinduced triplet depletion and demonstrated improved resolution of bright afterglow emission using the depletion. Triplet depletion is related to charge separation via photoionization from a triplet state caused by depletion and subsequent rapid singlet formation. Triplet excitons that accumulated in a solid material by excitation were depleted under irradiation using a depletion beam with a longer wavelength than the absorption wavelength of the material. A higher-resolution afterglow image with an improvement of 25% was obtained by simultaneously focusing a donut-shaped depletion beam and an excitation beam.
The persistent emission that remains after excitation light irradiation is stopped enables high-contrast imaging without relying on surrounding autofluorescence. However, the luminance of common persistent emitting materials hardly increases even when the excitation light intensity is increased. Therefore, they have not been utilized for emission imaging in the nano-sized regions. Here we introduce high-resolution afterglow imaging using long-lived room temperature phosphorescence (RTP), which remains strongly emitted after excitation light irradiation is stopped. While looking at the correlation between the estimated value based on a unique dynamic calculation and the experimental value regarding RTP performance, we designed and synthesized molecules that are expected to improve the quantum yield of long-lived RTP. The RTP yield of the designed molecules has been greatly improved, allowing afterglow detection from small objects independent of autofluorescence. We introduce examples of afterglow imaging, where the resolution and contrast change depending on the excitation light intensity.
Persistent room-temperature phosphorescence (pRTP) under ambient conditions is attracting attention due to its strong potential for state of art bioimaging and security applications because materials with pRTP can be utilized for high contrast emission imaging independent of autofluorescence using small-scale and low-cost photo-detectors. To extract efficient pRTP, the control of the radiative rate from the lowest triplet excited state (T1) (kp), the nonradiative rate of intramolecular vibrational relaxation at room temperature (RT) from T1 (knr(RT)), and the triplet quenching rate at RT caused by interactions with the ambient surroundings (kq(RT)) is crucial. In the last six years, knr(RT)+kq(RT) have been suppressed in a variety of heavy atom-free molecular materials under ambient conditions, which has allowed electrons in T1 to partly access the pRTP pathway with small kp. However, a key strategy to suppress knr(RT) and kq(RT) as well as increase kp for the efficient persistent RTP is not found yet.
Here, we investigate kp, knr(RT), and kq(RT) of heavy atom-free molecular materials showing pRTP. Cooperative analysis using microscope and quantum chemical calculation indicated that no appearance of pRTP of many heavy atom-free molecules are mostly caused by kq(RT) while minimization of the intermolecular triplet energy transfer using appropriate design of materials could largely decreased kq(RT). For knr(RT), analysis using vibrational spin–orbit coupling at RT indicates that knr(RT) of many heavy atom-free molecules is intrinsically small and approaches the small kp. To increase kp independent of knr(RT), the control of electronic structure of the high order excited state is highly important. This is first overall analysis of kp, knr(RT), and kq(RT) of heavy atom-free molecules, which will be important for realizing efficient pRTP from a variety of heavy atom-free molecular materials. In symposium, intrinsic characteristics of pRTP that general long persistent emitters could not reach are also explained.
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