Supramolecular Singlet Fission of Pentacene Dimers within Polyaromatic Capsules

Catti, Lorenzo; Narita, Haruna; Tanaka, Yuya; Sakai, Hayato; Hasobe, Taku; Tkachenko, Nikolai V.; Yoshizawa, Michito

doi:10.1021/jacs.0c13172

Cited by 23 publications

(22 citation statements)

References 58 publications

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“…This would give rise to the bathochromic band shift of 1b⊃PNT in the intramolecular transition region of PNT (Δλ max = +12 nm) in comparison with 1a⊃PNT (Figure 2a,b). 21 The band gap of the acene series decreases with an increase in the number of benzene rings. Long acenes have recently attracted increasing attention for their applications, such as novel laser materials and in vivo imaging, as the emission wavelength of acenes potentially approaches even the NIR region.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Nanoconfinement of an Otherwise Useless Fluorophore in Metal–Organic Frameworks to Elicit and Tune Emission

2022

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The rational design of the assembly of fluorophores is highly important for the fabrication of advanced nanomaterials.Here we report the encapsulation of pentacene (PNT) in the nanochannels of metal−organic frameworks (MOFs) as a powerful method to maximize properties of the fluorophore. Despite the nonemissive property of the bulk PNT, the nanoconfinement of PNT in MOFs drastically enhanced the luminescence, which enabled the precise tuning of the emission band approaching to the nearinfrared region. The luminescence of PNT was obviously changed concomitant with the adsorption of additional guests, which is beneficial to use the nanocomposites as a vapor sensor. Moreover, we demonstrated that the confined PNT exhibited exceptional stability (>100×) toward heat, in comparison with that in solution. The strong and intrinsic low-energy emission of long acenes together with the porous features of MOFs prompts the application of the MOF/acene hybrids targeting lighting devices, smart sensors, and in vivo imaging.

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Section: ■ Results and Discussionmentioning

confidence: 99%

Nanoconfinement of an Otherwise Useless Fluorophore in Metal–Organic Frameworks to Elicit and Tune Emission

2022

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“…As a general final perspective, in order to achieve a better control on micelles-substrate interactions for asymmetric induction, it is advisable the development of new rigid chiral surfactants bearing for instance large aromatic apolar surfaces. Such class of surfactants, inspired by the recent works of Yoshizawa, [97,98] will lead to the formation of micelles based on a small number of units. This will enable a better control of the reciprocal arrangement of the surfactant units, favoring positively the influence of the asymmetric environment provided by the aggregates in water.…”

Section: Discussionmentioning

confidence: 99%

Nanoconfinement Effects of Micellar Media in Asymmetric Catalysis

et al. 2022

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Replacement of organic solvents, in particular chlorinated, aromatic, and polar aprotic ones, is an emerging issue that can find a solution in the development of catalytic reactions in water. Nature performs a multitude of chemical transformations in water under mild conditions mediated by enzymes. In particular the nanoconfinement effects of the enzymes ensure high activity and impressive stereoselectivities. Micellar catalysis is nowadays a real alternative approach to catalysis in traditional organic media, enabling good activity under mild conditions, with the advantage of possible catalyst and micellar medium recycling. Micellar media emerged also as good nano‐environments for stereoselective reactions, with many examples of chemical transformations mediated by metal and organo‐catalysts for which improvements of stereoselectivity were observed with respect to the same reaction under homogeneous conditions in traditional organic solvents. More specifically, both the catalytically active site and the micelles provided by the surfactant can contribute to the asymmetric induction, partially resembling what known in terms of stereoselectivity imparted by the active site of enzymes and metallo‐enzymes.

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“…The associated supramolecular binding, of adequately high binding affinity, will append a change of free energy that is large enough to pay off the entropic penalty, thereby favoring the dimerization with preorganized and less diffusion-controlled features. A broad range of supramolecular dimers have been achieved by association with various types of supramolecular binding events such as macrocyclic complexations, , capsulation through hydrogen bonding, or halogen and chalcogen bonding, antielectrostatic hydrogen bonding, − metal-coordination, − metal–metal interaction, micellization, , and so on. This Perspective mainly employs macrocyclic-based, particularly cucurbituril-based, host–guest systems to exemplify the molecular engineering of supramolecular dimerization.…”

Section: Supramolecular Dimerizationmentioning

confidence: 99%

Molecular Engineering of Noncovalent Dimerization

Tang

et al. 2022

J. Am. Chem. Soc.

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Dimers are probably the simplest model to facilitate the understanding of fundamental physical and chemical processes that take place in much-expanded systems like aggregates, crystals, and other solid states. The molecular interplay within a dimer differentiates it from the corresponding monomeric state and determines its features. Molecular engineering of noncovalent dimerization through applied supramolecular restrictions enables additional control over molecular interplay, particularly over its dynamic aspect. This Perspective introduces the recent effort that has been made in the molecular engineering of noncovalent dimerization, including supramolecular dimers, folda-dimers, and macrocyclic dimers. It showcases how the variation in supramolecular restrictions endows molecular-based materials with improved performance and/or functions like enhanced emission, room-temperature phosphorescence, and effective catalysis. We particularly discuss pseudostatic dimers that can sustain molecular interplay for a long period of time, yet are still flexible enough to adapt to variations. The pseudostatic feature allows for active species to decay along an alternate pathway, thereby spinning off emerging features that are not readily accessible from conventional dynamic systems.

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Supramolecular Singlet Fission of Pentacene Dimers within Polyaromatic Capsules

Cited by 23 publications

References 58 publications

Nanoconfinement of an Otherwise Useless Fluorophore in Metal–Organic Frameworks to Elicit and Tune Emission

Nanoconfinement of an Otherwise Useless Fluorophore in Metal–Organic Frameworks to Elicit and Tune Emission

Nanoconfinement Effects of Micellar Media in Asymmetric Catalysis

Molecular Engineering of Noncovalent Dimerization

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