Symmetry breaking and the turn-on fluorescence of small, highly strained carbon nanohoops

Lovell, Terri C.; Colwell, Curtis; Zakharov, Lev N.; Jasti, Ramesh

doi:10.1039/c9sc00169g

Cited by 119 publications

(241 citation statements)

References 38 publications

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“…This value is higher than that observed in [4]C-diEt-F for which the angle is zero. [7] The mean torsion angle appearsherein as high as 40.68 (values comprised between 38.38 and 42.358,F igure S24), which is similar to that measured in [4]C-diEt-F (41.58 between two fluorene units) [30] and significantly higher than that of [8]CPP (24.38 between two phenyl units, Figure S29). Thus, the nitrogen bridge provides more structural flexibility than the carbon bridge in an anoringc onstituted of four units.…”

Section: Resultssupporting

confidence: 68%

“…[2][3][4][5][6] Compared to their linearc ounterparts, nanorings present singular electronic and structuralc haracteristics. [3][4][5][6][7] In addition, studies on the influence of the nanoring size and of the building units on the structural, electronic, physical, chiral and encapsulating properties have already shown the diversity of this field. [3][4][5][6][7][8] The growinginterestinnanorings chemistry and physics has led to recent applications such as imaging tools in biology [9] or complexation of single-walledc arbonn anotubes.…”

Section: Introductionmentioning

confidence: 99%

“…[3][4][5][6][7] In addition, studies on the influence of the nanoring size and of the building units on the structural, electronic, physical, chiral and encapsulating properties have already shown the diversity of this field. [3][4][5][6][7][8] The growinginterestinnanorings chemistry and physics has led to recent applications such as imaging tools in biology [9] or complexation of single-walledc arbonn anotubes. [10] In 2016, Nuckolls and co-workers have shown the severala dvantages of cyclic oligomers over corresponding linear counterparts in electronics devices.…”

Section: Introductionmentioning

confidence: 99%

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[4]Cyclo‐N‐ethyl‐2,7‐carbazole: Synthesis, Structural, Electronic and Charge Transport Properties

Lucas

Sicard

Jeannin

et al. 2019

Chemistry A European J

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Nanorings, which are macrocyclesp ossessing radially directed p-orbitalsh ave shown fantastic developmenti n the last ten years. Unravelling their unusuale lectronicp roperties has been one of the driving forces of this research field. However,a nd despite promising properties, their incorporationi no rganic electronic devices remains very scarce. In this work, we aim to contribute to bridge the gap between organice lectronics and nanorings by reporting the synthesis, the structurala nd electronic properties and the incorporation in an organic field-effect transistor (OFET) of ac yclic tetracarbazole, namely[ 4]cyclo-N-ethyl-2,7-carbazole( [4]C-Et-Cbz). The structural, photophysicala nd electrochemical properties have been compared to those of structurally related analogues [4]cyclo-9,9-diethyl-2,7-fluorene [4]C-diEt-F (with carbon bridges) and [8]-cycloparaphenylene [8]CPP (withouta ny bridge) in ordert os hed light on the impact of the bridging in nanorings. This work shows that nanorings can be used as an active layer in an OFET and provides a first benchmark in term of OFET characteristicsf or this type of molecules.

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Section: Resultssupporting

confidence: 68%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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[4]Cyclo‐N‐ethyl‐2,7‐carbazole: Synthesis, Structural, Electronic and Charge Transport Properties

Lucas

Sicard

Jeannin

et al. 2019

Chemistry A European J

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“…Additionally, as a consequence of breaking molecular orbital symmetry, it should be noted that both 3 and 4 were fluorescent, with 3 emitting at λ max of 509 nm ( Φ =0.14) and 4 at λ max of 476 nm ( Φ =0.62). Of note, the all para ‐substituted nanohoop with a single embedded pyridine is non‐emissive; a detailed investigation of the result of symmetry breaking on nanohoop fluorescence is disclosed in a separate study …”

Section: Figurementioning

confidence: 99%

Nanohoop Rotaxanes from Active Metal Template Syntheses and Their Potential in Sensing Applications

et al. 2019

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The unique optoelectronic properties and smooth, rigid pores of macrocycles with radially oriented p systems render them fascinating candidates for the design of novel mechanically interlocked molecules with new properties.T wo high-yielding strategies are used to prepare nanohoop [2]rotaxanes,which owing to the p-rich macrocycle are highly emissive. Then, metal coordination, an intrinsic property afforded by the resulting mechanical bond, can lead to molecular shuttling as well as modulate the observed fluorescence in both organic and aqueous conditions.Inspired by these findings,aself-immolative [2]rotaxane was then designed that self-destructs in the presence of an analyte,e liciting as trong fluorescent turn-on response,s erving as proof-of-concept for an ew type of molecular sensing material. More broadly,this work highlights the conceptual advantages of combining compact p-rich macrocyclic frameworks with mechanical bonds formed via active-template syntheses.

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“…[27,28] Finally, most CPPs are brighter than similar emitting smallmolecule fluorophores, they retain their fluorescent properties in aqueous media, have minimal cytotoxicity and are cell permeable making them attractive as novel biological fluorophores. [7,18,29,30] However, bright CPPs with emissions beyond 500 nm have yet to be realized. CPP fluorescence red-shifts as the size of the nanohoop decreases, however, decreasing size leads to a dramatic decrease in quantum yield due to strain and orbital-symmetry rules.…”

mentioning

confidence: 99%

Synthesis, Characterization, and Computational Investigation of Bright Orange‐Emitting Benzothiadiazole [10]Cycloparaphenylene

2020

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Conjugated aromatic macrocycles are attractive due to their unique photophysical and optoelectronic properties. In particular, the cyclic radially oriented π‐system of cycloparaphenylenes (CPPs) gives rise to photophysical properties unlike any other small molecule or carbon nanomaterial. CPPs have tunable emission, possess large extinction coefficients, wide effective Stokes shifts, and high quantum yields. However, accessing bright CPPs with emissions beyond 500 nm remains difficult. Herein, we present a novel and bright orange‐emitting CPP‐based fluorophore showing a dramatic 105 nm red‐shift in emission and striking 237 nm effective Stokes shift while retaining a large quantum yield of 0.59. We postulate, and experimentally and theoretically support, that the quantum yield remains large due to the lack of intramolecular charge transfer.

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Symmetry breaking and the turn-on fluorescence of small, highly strained carbon nanohoops

Abstract: By breaking the centrosymmetry of the structure, the most strained carbon nanohoops become fluorescent as predicted by optical selection rules.

Cited by 119 publications

References 38 publications

[4]Cyclo‐N‐ethyl‐2,7‐carbazole: Synthesis, Structural, Electronic and Charge Transport Properties

[4]Cyclo‐N‐ethyl‐2,7‐carbazole: Synthesis, Structural, Electronic and Charge Transport Properties

Nanohoop Rotaxanes from Active Metal Template Syntheses and Their Potential in Sensing Applications

Synthesis, Characterization, and Computational Investigation of Bright Orange‐Emitting Benzothiadiazole [10]Cycloparaphenylene

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