Enhanced Triplet–Triplet Energy Transfer and Upconversion Fluorescence through Host–Guest Complexation

Fan, Chunying; Wu, Wanhua; Chruma, Jason J.; Zhao, Jianzhang; Yang, Cheng

doi:10.1021/jacs.6b07946

Cited by 165 publications

(114 citation statements)

References 97 publications

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“…Stimuli‐responsive nanosystems formed by multicomponent supramolecular self‐organization are of great interest, due to their simple composition, easy adjustability, and good reproducibility. As one of the most important photophysical tools in stimuli‐responsive photoluminescent materials, energy transfer (ET) has been widely applied in biological sensing, photodynamic therapy, photocontrolling the generation of singlet oxygen, upconversion luminescent devices, and light‐tunable fluorescent supramolecular systems . Among various fluorophores to achieve ET process applied in biological sensing, near‐infrared (NIR) fluorochromes are preferred for imaging living cells and tissues, because they offer low phototoxicity to cells, minimal interference by the hemoglobin absorption, low autofluorescence, and good tissue penetration .…”

Section: Methodsmentioning

confidence: 99%

Controllable Photoluminescence Behaviors of Amphiphilic Porphyrin Supramolecular Assembly Mediated by Cyclodextrins

Liu

Zhang

et al. 2017

Advanced Optical Materials

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and ubiquity, compared with other various external stimuli. [7] Therefore, the combination of light input and NIR labels is expected to provide a new quick access to the fabrication of advanced optically functional materials. However, constructing photoadjustable NIR photoluminescent nanosystem that incorporates multiple NIR fluorochromes and works in aqueous media is not an easy task and, indeed, has never been achieved, to the best of our knowledge.In the present work, we employed supramolecular methodology to construct a photoresponsive nanoassembly that emits photochemically switchable NIR fluorescence in water. Our rationally designed ternary nanosystem, incorporating dithienylethene, porphyrin, and cyanine dye as the essential components, has several inherent advantages: (1) Dithienylethenes can undergo reversible cyclization/ cycloreversion upon distinct light irradiation and constitute a key component in photoswitchable molecular devices, [8] (2) Porphyrins, often used as photosensitizers in biomedical field, can be supramolecularly functionalized by the noncovalent association with permethyl-β-cyclodextrins (PMCD); [9] (3) Cyanine dye-5 (Cy) is an excellent NIR fluorochrome frequently used in cellular imaging because of its chemical stability and high fluorescence quantum yield. [10] Thus, the rational conjugation of these components is expected to bring about a breakthrough in photoswitchable biomaterials. In our approach to realize such an intelligent system, the above-mentioned modules were incorporated in a sophisticated manner to create an unprecedented light-responsive supramolecular assembly that exhibits reversible photoswitching fluorescence resonance energy transfer (FRET) behaviors in the NIR region (Scheme 1).Dithienylethene-bridged bis(permethyl-β-CD)s (1) (Scheme S1 and Figures S1-S4, Supporting Information) exhibited excellent photochromism reversibility in water. As shown in Figure 1a, the open-form of the molecular switch (OF-1) gave an absorption maximum at 292 nm (ε = 4.36 × 10 4 L mol −1 cm −1 ), while a new absorption peak appeared at 592 nm (ε = 1.58 × 10 4 m −1 cm −1 ) with an isosbestic point at 319 nm upon UV irradiation at 254 nm with accompanying color change from colorless to blue (Figure 1a, inset), as a consequence of the photocyclization of the dithienylethene moiety to the closed-form (CF-1). The Tunable photoluminescence nanomaterials have aroused increasing interest from researchers recently due to their application in bioimaging, photodynamic therapy, and energy conversion. Herein, an artificial ternary nanosystem comprised of dithienylethene-bridged bis(permethyl-β-CD)s, dodecyl-bearing porphyrin, and amphipathic near-infrared (NIR) cyanine fluorochrome is conveniently constructed by rationally designing the host/guest components, dimensions, and properties. In this system, an effective energy transfer (ET) from porphyrin to cyanine fluorochrome leads to the dramatic enhancement of NIR fluorescence intensity and more crucially, this process can be efficiently regulat...

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Section: Methodsmentioning

confidence: 99%

Controllable Photoluminescence Behaviors of Amphiphilic Porphyrin Supramolecular Assembly Mediated by Cyclodextrins

Liu

Zhang

et al. 2017

Advanced Optical Materials

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“…One approach is to develop large supra-molecular structures where TET and TTA can occur intra-molecularly, overcoming the diffusion limit. 26 In such a supra-molecular system the sensitizer must be in close proximity to an annihilator. One advantage of ruthenium porphyrins, compared to the palladium and platinum analogues, is that pyridine ligands can coordinate to the ruthenium atom.…”

Section: Ruoep(co)-ligand Complexes Applied To Triplet-triplet Annihimentioning

confidence: 99%

“…[22][23][24] Engineered photosynthetic systems with increased efficiencies will require even greater oxygen protection, motivating further exploration of TET in model porphyrin donor-acceptor systems. 24 Furthermore, in the development of supramolecular structures designed for photochemical applications, such as triplet-triplet annihilation based photon upconversion [25][26][27] or photocatalysis [28][29][30] the delicate balance between energy and electron transfer reactions requires careful tuning.…”

mentioning

confidence: 99%

Singlet and triplet energy transfer dynamics in self-assembled axial porphyrin–anthracene complexes: towards supra-molecular structures for photon upconversion

Gray

Küçüköz

Edhborg

et al. 2018

Phys. Chem. Chem. Phys.

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Energy and electron transfer reactions are central to many different processes and research fields, from photosynthesis and solar energy harvesting to biological and medical applications. Herein we report a comprehensive study of the singlet and triplet energy transfer dynamics in porphyrin-anthracene coordination complexes. Seven newly synthesized pyridine functionalized anthracene ligands, five with various bridge lengths and two dendrimer structures containing three and seven anthracene units, were prepared. We found that triplet energy transfer from ruthenium octaethylporphyrin to an axially coordinated anthracene is possible, and is in some cases followed by back triplet energy transfer to the porphyrin. The triplet energy transfer follows an exponential distance dependence with an attenuation factor, β, of 0.64 Å. Further, singlet energy transfer from anthracene to the ruthenium porphyrin appears to follow a R Förster distance dependence. Porphyrin-anthracene complexes are also used as triplet sensitizers for triplet-triplet annihilation (TTA) based photon upconversion, demonstrating their potential for photophysical and photochemical applications. The triplet lifetime of the complex is extended by the anthracene ligands, resulting in a threefold increase in the upconversion efficiency, Φ to 4.5%, compared to the corresponding ruthenium porphyrin-pyridine complex. Based on the results herein we discuss the future design of supra-molecular structures for TTA upconversion.

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“…Unsubstituted buckybowls 1 and 2 are not chiral due to the presence of the reflection symmetry with respect to the mirror planes containing the rotational axis to show C 5v and C 3v symmetry, respectively. Introducing the addends may break the reflection symmetry to cause chirality, and alter their properties, such as bowl-to-bowl inversion [12][13][14][15][16][17][18][19][20][21][22], chirality [12,17,19,23], bowl depth [14,19,20], crystal structure [19,24,25], molecular recognition [2,26,27,51] and supramolecular assembly [3,[28][29][30]52,53] behavior, metal complexation [23,[31][32][33][34][35][36], electronic conductivity [19,37,38], and so on. Although the chirality is an important element in three-dimensional curved π-electron systems, thus far there have been no reports of the enantioselective synthetic control of the bowl chirality.…”

Section: Stereodescriptor System Of Buckybowlsmentioning

confidence: 99%

Chiral Buckybowl Molecules

Kanagaraj

Lin

et al. 2017

Symmetry

Self Cite

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Buckybowls are polynuclear aromatic hydrocarbons that have a curved aromatic surface and are considered fragments of buckminsterfullerenes. The curved aromatic surface led to the loss of planar symmetry of the normal aromatic plane and may cause unique inherent chirality, so-called bowl chirality, which it is possible to thermally racemize through a bowl-to-bowl inversion process. In this short review, we summarize the studies concerning the special field of bowl chirality, focusing on recent practical aspects of attaining diastereo/enantioenriched chiral buckybowls through asymmetric synthesis, chiral optical resolution, selective chiral metal complexation, and chiral assembly formation.

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Enhanced Triplet–Triplet Energy Transfer and Upconversion Fluorescence through Host–Guest Complexation

Cited by 165 publications

References 97 publications

Controllable Photoluminescence Behaviors of Amphiphilic Porphyrin Supramolecular Assembly Mediated by Cyclodextrins

Controllable Photoluminescence Behaviors of Amphiphilic Porphyrin Supramolecular Assembly Mediated by Cyclodextrins

Singlet and triplet energy transfer dynamics in self-assembled axial porphyrin–anthracene complexes: towards supra-molecular structures for photon upconversion

Chiral Buckybowl Molecules

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