Pt(Ⅱ)-salophen complexes(S-1~S-4) and 9,10-diphenylanthracene(DPA) tethering pillar[5]arene derivatives(A-1 and A-2) were synthesized to act as sensitizers and annihilators for triplet-triplet annihilation upconversi...Pt(Ⅱ)-salophen complexes(S-1~S-4) and 9,10-diphenylanthracene(DPA) tethering pillar[5]arene derivatives(A-1 and A-2) were synthesized to act as sensitizers and annihilators for triplet-triplet annihilation upconversion(TTA-UC), respectively. It turned out that the pyridine cation served as a mask for the excited state of the sensitizer, the triplet states of S-2 and S-3 were significantly quenched by photo-induced electron transfer(PET) with phosphorescence quantum yield quenched from 24.4% for S-4 to 9.3% for S-3,and therefore, both S-2 and S-3 led to negligible UC emissions when traditional annihilator DPA was used as the annihilator. Delightfully, when supramolecular annihilator A-1 and A-2 were employed to include the pyridine cation, PET was significantly inhibited and the triplet states of the sensitizers were activated,TTA-UC emission was therefore boosted. The UC quantum yield of A-2/S-3 system was up to 130 times higher than that of DPA/S-3 system, and the UC emission was switchable by the addition of competitive vips.展开更多
Triplet-triplet annihilation(TTA) upconversion-based materials have potential application in the broad range of research areas, including photocatalysis and life sciences. However, near-infrared(NIR)-to-blue upconvert...Triplet-triplet annihilation(TTA) upconversion-based materials have potential application in the broad range of research areas, including photocatalysis and life sciences. However, near-infrared(NIR)-to-blue upconverted emission is preferred for most of the practical applications, but developing a NIR-to-blue TTA upconversion system is a challenging task in photochemistry. In this work, a thermally activated delayed fluorescence(TADF) material with intense visible-to-NIR absorption is demonstrated that shows a longer triplet state lifetime(32 μs) and high triplet state energy(E_(T)= 1.55 e V). For the first time, a heavy atomfree NIR(λ_(ex)> 650 nm) to blue(λ_(em)< 460 nm) TTA upconversion system was devised, employing the dimeric borondifluoride curcuminoid TADF material as triplet photosensitizer(PS) and a large anti-Stokes shift(0.88 e V) along with moderate upconversion yield was achieved. Our work provides the solution and guidance for the future development of purely organic heavy atom-free NIR activating TTA upconversion system for a wide array of applications.展开更多
基金supported by the National Natural Science Foundation of China (Nos. 22171194, 21971169, 92056116 and 21871194)the Fundamental Research Funds for the Central Universities (No. 20826041D4117)the Science & Technology Department of Sichuan Province (Nos. 2022YFH0095 and 2021ZYD0052)。
文摘Pt(Ⅱ)-salophen complexes(S-1~S-4) and 9,10-diphenylanthracene(DPA) tethering pillar[5]arene derivatives(A-1 and A-2) were synthesized to act as sensitizers and annihilators for triplet-triplet annihilation upconversion(TTA-UC), respectively. It turned out that the pyridine cation served as a mask for the excited state of the sensitizer, the triplet states of S-2 and S-3 were significantly quenched by photo-induced electron transfer(PET) with phosphorescence quantum yield quenched from 24.4% for S-4 to 9.3% for S-3,and therefore, both S-2 and S-3 led to negligible UC emissions when traditional annihilator DPA was used as the annihilator. Delightfully, when supramolecular annihilator A-1 and A-2 were employed to include the pyridine cation, PET was significantly inhibited and the triplet states of the sensitizers were activated,TTA-UC emission was therefore boosted. The UC quantum yield of A-2/S-3 system was up to 130 times higher than that of DPA/S-3 system, and the UC emission was switchable by the addition of competitive vips.
基金the National Natural Science Foundation of China (Nos. 21975053, 21975055, U2001222)Guangdong Basic and Applied Basic Research Foundation (Nos. 2019B1515120023, 2022B1515020041)Guangdong Province Universities and Colleges Pearl River Scholar Funded Scheme (2019) for financial support。
文摘Triplet-triplet annihilation(TTA) upconversion-based materials have potential application in the broad range of research areas, including photocatalysis and life sciences. However, near-infrared(NIR)-to-blue upconverted emission is preferred for most of the practical applications, but developing a NIR-to-blue TTA upconversion system is a challenging task in photochemistry. In this work, a thermally activated delayed fluorescence(TADF) material with intense visible-to-NIR absorption is demonstrated that shows a longer triplet state lifetime(32 μs) and high triplet state energy(E_(T)= 1.55 e V). For the first time, a heavy atomfree NIR(λ_(ex)> 650 nm) to blue(λ_(em)< 460 nm) TTA upconversion system was devised, employing the dimeric borondifluoride curcuminoid TADF material as triplet photosensitizer(PS) and a large anti-Stokes shift(0.88 e V) along with moderate upconversion yield was achieved. Our work provides the solution and guidance for the future development of purely organic heavy atom-free NIR activating TTA upconversion system for a wide array of applications.
