Mechanically interlocked pyrene-based photocatalysts

Garci, Amine; Weber, Jacob A.; Young, Ryan M.; Kazem‐Rostami, Masoud; Ovalle, Marco; Beldjoudi, Yassine; Atilgan, Ahmet; Bae, Youn Jue; Liu, Wenqi; Jones, Leighton O.; Stern, Charlotte L.; Schatz, George C.; Farha, Omar K.; Wasielewski, Michael R.

doi:10.1038/s41929-022-00799-y

Cited by 37 publications

(25 citation statements)

References 60 publications

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“…The dynamic behavior of the thermostable 2,7−2,7 PyHC 8+ has been investigated previously 16 by 1 H NMR spectroscopy in three different solvents�namely, CD 3 CN, MeOD, and D 2 O. In the present investigation the relative coconformational motions of the cyclophanes in this [2]catenane were investigated in DMF-d 7 by VT 1 H NMR spectroscopy.…”

Section: ■ Results and Discussionmentioning

confidence: 98%

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Thermally Controlled Exciplex Fluorescence in a Dynamic Homo[2]catenane

et al. 2022

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Motion-induced change in emission (MICE) is a phenomenon that can be employed to develop various types of probes, including temperature and viscosity sensors. Although MICE, arising from the conformational motion in particular compounds, has been studied extensively, this phenomenon has not been investigated in depth in mechanically interlocked molecules (MIMs) undergoing coconformational changes. Herein, we report the investigation of a thermoresponsive dynamic homo[2]catenane incorporating pyrene units and displaying relative circumrotational motions of its cyclophanes as evidenced by variable-temperature 1 H NMR spectroscopy and supported by its visualization through molecular dynamics simulations and quantum mechanics calculations. The relative coconformational motions induce a significant change in the fluorescence emission of the homo[2]catenane upon changes in temperature compared with its component cyclophanes. This variation in the exciplex emission of the homo[2]catenane is reversible as demonstrated by four complete cooling and heating cycles. This research opens up possibilities of using the coconformational changes in MIMs-based chromophores for probing fluctuations in temperature which could lead to applications in biomedicine or materials science.

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Section: ■ Results and Discussionmentioning

confidence: 98%

“… a The rate was calculated employing the Eyring equation (Figure S3 and ref ). b This value is extrapolated because it is above the boiling point of the solvent. …”

Section: Resultsmentioning

confidence: 99%

Thermally Controlled Exciplex Fluorescence in a Dynamic Homo[2]catenane

et al. 2022

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“…17 Although numerous catalysts have been presented in the literature for mild and selective oxidation of thioethers to sulfoxides, 18 a few have performed the oxidation photocatalytically with the use of mechanically interlocked molecular machines. 12,19 For this purpose, methionine was chosen as a chiral substrate for its known oxidation mechanism 12 and its possible interactions with TBAs. In order to monitor the progress of the photocatalytic aerobic oxidations a reversed-phase chiral HPLC method was chosen that separates the two enantiomers of methionine from one another and methionine sulfoxides.…”

Section: Resultsmentioning

confidence: 99%

A nitrogen-based chiral catenane for enantioenriching photocatalytic aerobic oxidation

Kazem‐Rostami

2022

New J. Chem.

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“…Extended bipyridinium-based cyclophanes − (Ex n Box 4+ ) and their π-conjugated analogues − have been investigated extensively by us in the past. We consider box-like fluorescent tetracationic cyclophanes to be good candidates for biological imaging because of the excellent water solubility of their chloride salts and low cytotoxicity profiles based on our own previous investigations − carried out on tetra- and octacationic fluorescent cyclophanes, cages, , and catenanes. − …”

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confidence: 99%

Alkoxy-Substituted Quadrupolar Fluorescent Dyes

et al. 2022

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Polar and polarizable π-conjugated organic molecules containing push−pull chromophores have been investigated extensively in the past. Identifying unique backbones and building blocks for fluorescent dyes is a timely exercise. Here, we report the synthesis and characterization of a series of fluorescent dyes containing quadrupolar A−D−A constitutions (where A = acceptor and D = donor), which exhibit fluorescence emission at a variety of different wavelengths. We have investigated the effects of different electron-withdrawing groups, located at both termini of a para-terphenylene backbone, by steady-state UV/vis and fluorescence spectroscopy. Pyridine and substituted pyridinium units are also introduced during the construction of the quadrupolar backbones. Depending on the quadrupolarity, fluorescence emission wavelengths cover from 380 to 557 nm. Time-resolved absorption and emission spectroscopy reveal that the photophysical properties of those quadrupolar dyes result from intramolecular charge transfer. One of the dyes we have investigated is a symmetrical box-like tetracationic cyclophane. Its water-soluble tetrachloride, which is non-cytotoxic to cells up to a loading concentration of 1 μM, has been employed in live-cell imaging. When taken up by cells, the tetrachloride emits a green fluorescence emission without any hint of photobleaching or disruption of normal cell behavior. We envision that our design strategy of modifying molecules through the functionalization of the quadrupolar building blocks as chromophores will lead to future generations of fluorescent dyes in which these A−D−A constitutional fragments are incorporated into more complex molecules and polymers for broader photophysical and biological applications.

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Mechanically interlocked pyrene-based photocatalysts

Cited by 37 publications

References 60 publications

Thermally Controlled Exciplex Fluorescence in a Dynamic Homo[2]catenane

Thermally Controlled Exciplex Fluorescence in a Dynamic Homo[2]catenane

A nitrogen-based chiral catenane for enantioenriching photocatalytic aerobic oxidation

Alkoxy-Substituted Quadrupolar Fluorescent Dyes

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