Stimuli‐Responsive Dual‐Color Photon Upconversion: A Singlet‐to‐Triplet Absorption Sensitizer in a Soft Luminescent Cyclophane

Mase, Kazuma; Sasaki, Yōichi; Sagara, Yasuyuki; Tamaoki, Nobuyuki; Weder, Christoph; Yanai, Nobuhiro; Kimizuka, Nobuo

doi:10.1002/ange.201712644

Cited by 12 publications

(3 citation statements)

References 56 publications

(15 reference statements)

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“…Such an extra NIR absorbance corresponds to an unusual direct S 0 → T n transition that is typically spin-forbidden in organic molecular chromophore systems. Due to the forbidden nature of the immediate optical transition between the spin-zero ground (S 0 ) state and the spin-one triplet (T 1 ) levels, molecular triplet exciton is a dark state with no direct triplet absorption 29,30 . However, pioneering works that couple organic excimers with unpaired spins of heavy atoms such as Lanthanide enable a bright triplet NIR absorption through the triplet energy transfer [21][22][23][24][25]29,30 .…”

Section: Synthesis and Catalyst Structurementioning

confidence: 99%

“…Due to the forbidden nature of the immediate optical transition between the spin-zero ground (S 0 ) state and the spin-one triplet (T 1 ) levels, molecular triplet exciton is a dark state with no direct triplet absorption 29,30 . However, pioneering works that couple organic excimers with unpaired spins of heavy atoms such as Lanthanide enable a bright triplet NIR absorption through the triplet energy transfer [21][22][23][24][25]29,30 . In our system, the NIR absorption occurs in the interval of enhanced triplet spin-orbit coupling (72~96 h) (Fig.…”

Section: Synthesis and Catalyst Structurementioning

confidence: 99%

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Solar overall water-splitting by a spin-hybrid all-organic semiconductor

Lin,

Hao,

Gong

et al. 2024

Nat Commun

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Direct solar-to-hydrogen conversion from pure water using all-organic heterogeneous catalysts remains elusive. The challenges are twofold: (i) full-band low-frequent photons in the solar spectrum cannot be harnessed into a unified S1 excited state for water-splitting based on the common Kasha-allowed S0 → S1 excitation; (ii) the H+ → H2 evolution suffers the high overpotential on pristine organic surfaces. Here, we report an organic molecular crystal nanobelt through the self-assembly of spin-one open-shell perylene diimide diradical anions (:PDI2-) and their tautomeric spin-zero closed-shell quinoid isomers (PDI2-). The self-assembled :PDI2-/PDI2- crystal nanobelt alters the spin-dependent excitation evolution, leading to spin-allowed S0S1 → 1(TT) → T1 + T1 singlet fission under visible-light (420 nm~700 nm) and a spin-forbidden S0 → T1 transition under near-infrared (700 nm~1100 nm) within spin-hybrid chromophores. With a triplet-triplet annihilation upconversion, a newly formed S1 excited state on the diradical-quinoid hybrid induces the H+ reduction through a favorable hydrophilic diradical-mediated electron transfer, which enables simultaneous H2 and O2 production from pure water with an average apparent quantum yield over 1.5% under the visible to near-infrared solar spectrum.

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Section: Synthesis and Catalyst Structurementioning

confidence: 99%

Section: Synthesis and Catalyst Structurementioning

confidence: 99%

Solar overall water-splitting by a spin-hybrid all-organic semiconductor

Lin,

Hao,

Gong

et al. 2024

Nat Commun

View full text Add to dashboard Cite

show abstract

“…Such an extra NIR absorbance corresponds to an unusual direct S 0 →T n transition that is typically spin-forbidden in organic molecular chromophore systems. Due to the forbidden nature of the immediate optical transition between the spinzero ground (S 0 ) state and the spin-one triplet (T 1 ) levels, molecular triplet exciton is a dark state with no direct triplet absorption 29,30 . However, pioneering works that couple organic excimers with unpaired spins of heavy atoms such as Lanthanide enable a bright triplet NIR absorption through the triplet energy transfer 21-25, 29, 30 .…”

Section: Synthesis and Catalyst Structurementioning

confidence: 99%

Solar overall water-splitting by a spin-hybrid all-organic semiconductor

Lin

Hao

Gong

et al. 2023

Preprint

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Direct solar-to-hydrogen (STH) conversion from pure water using all-organic heterogeneous catalysts remains elusive. The challenges are twofold: (i) full-band low-frequent photons in the solar spectrum cannot be harnessed into a unified S1 excited state for water-splitting based on the common Kasha-allowed S0→S1 excitation; (ii) the H+→H2 evolution suffers the high overpotential on pristine organic surfaces. Here, we report an organic molecular crystal nanobelt through the self-assembly of spin-one open-shell perylene diimide diradical anions (:PDI2−) and their tautomeric spin-zero closed-shell quinoid isomers (PDI2−). The self-assembled :PDI2−/PDI2− crystal nanobelt alters the spin-dependent excitation evolution, leading to spin-allowed S0S1→1(TT)→T1 + T1 singlet fission under visible-light (420 nm ~ 700 nm) and a spin-forbidden S0→T1 transition under NIR (700 nm ~ 1100 nm) within spin-hybrid chromophores. With a triplet-triplet annihilation upconversion, a newly formed S1 excited state on the diradical-quinoid hybrid induces the H+ reduction through a favorable hydrophilic diradical-mediated electron transfer, which enables simultaneous H2 and O2 production from pure water with an average apparent quantum yield over 1.5% under the visible-to-NIR solar spectrum.

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Hybrid Chloroantimonates(III): Thermally Induced Triple‐Mode Reversible Luminescent Switching and Laser‐Printable Rewritable Luminescent Paper

et al. 2019

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Tw ohybrid chloroantimonates(III), [Bzmim] 3 SbCl 6 (1,B zmim = 1-benzyl-3-methylimidazolium, T m1 = 410 K) and [Bzmim] 2 SbCl 5 (2,T m2 = 348 K) are presented. 1 exhibits green emission (quantum efficiency of 87.5 %); 2 exhibits blue and red emissions under the irradiation of 310 and 396 nm light, respectively.Using different cooling methods,crystalline 1 and IL@2 (IL = ionic liquid of [Bzmim]Cl) could be generated from the molten 1.R eversible structural and PL transformation triggered by moisture or heat was observed between 1 and IL@2.S uchP Ls witching,c ombined with the crystallization-induced PL properties of 1 and 2,resulted in the firstly reported triple-mode reversible PL switching,that is,onoff (T > T m1 ), color switching (T < T m2 ), and on-off-on (T m2 < T < T m1 ). Furthermore,i nk-and mask-free laser-printable rewritable PL paper was achieved. This study demonstrates the promise of dynamic insertion/extraction of ILs in hybrid chloroantimonates for anti-counterfeiting and rewritable PL paper.Supportinginformation (including the experimental section, synthesis methods, single-crystalX-ray data, more structurald etails, UV/Vis spectra, PXRD patterns, FTIR spectra, TG curves) and the ORCID identification number(s) for the author(s) of this article can be found under: https://doi.

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Stimuli‐Responsive Dual‐Color Photon Upconversion: A Singlet‐to‐Triplet Absorption Sensitizer in a Soft Luminescent Cyclophane

Cited by 12 publications

References 56 publications

Solar overall water-splitting by a spin-hybrid all-organic semiconductor

Solar overall water-splitting by a spin-hybrid all-organic semiconductor

Solar overall water-splitting by a spin-hybrid all-organic semiconductor

Hybrid Chloroantimonates(III): Thermally Induced Triple‐Mode Reversible Luminescent Switching and Laser‐Printable Rewritable Luminescent Paper

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