A new fundamental type of conformational isomerism

Canfield, P.J.; Blake, Iain M.; Cai, Zheng-Li; Luck, Ian J.; Krausz, Elmars; Kobayashi, Rika; Reimers, Jeffrey R.; Crossley, Maxwell J.

doi:10.1038/s41557-018-0043-6

Cited by 47 publications

(76 citation statements)

References 88 publications

(81 reference statements)

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“…Stable structures were predicted for four complexes S a S p , S p S a , S a R a , and S p R p (Figure and Figure S1 in the Supporting Information). Several significant differences compared with previously reported difluoro derivatives of quinoxalinoporphyrin should be noted. First, in contrast to difluoro structures, where only one cisoid isomer was identified, we succeeded in finding the minima on the potential energy surface (PES) for both cisoid akamptisomers containing fullerene fragments.…”

Section: Resultsmentioning

confidence: 99%

“…Second, the interaction of C 60 and porphyrin stabilizes S a S p compared with S p S a by 6.9 kcal mol −1 . By contrast, the corresponding difluoro derivatives have the same energy …”

Section: Resultsmentioning

confidence: 99%

“…Structure and relative stability of the akamptisomers As already noted, the boron atoms being the R and S centers in the complexes enable the existence of akamptisomers. [39] The eight possible stereoisomers can be grouped into four pairs of enantiomers with indistinguishable physical properties (except for their interaction with polarized light). Thus, we will consider only four stereoisomers (one from each pair).…”

Section: Resultsmentioning

confidence: 99%

“…Second, the interaction of C 60 and porphyrin stabilizes S a S p compared with S p S a by 6.9 kcal mol À1 .B yc ontrast, the corresponding difluoro derivatives have the same energy. [39] To understand the lower energy of S p R p and S a S p compared with S a R a and S p S a ,Q TAIM calculations [45] were performed.I n the transoid S a S p isomer,t he strongesti nteractionsa re found between C 60 and quinoxaline andb etween C 60 and mesophenyl( see Figure S2 in the Supporting Information). At the same time, in the S p S a isomer,o ne fullerene (lying below qui-noxalinei nF igure 1) is not involved in non-covalent interactions, whereas the other fullerenef ragment demonstrates notable interaction with the meso-phenyl ring.…”

Section: Resultsmentioning

confidence: 99%

“…have discovered an ew type of isomerism calleda kamptisomerism. [39] New descriptors parvo and amplo (from Latin "small" and "large") have been introduced to describe the corresponding isomers. Four akamptisomers of FB-O-BF-quinoxalinoporphyrin were described.…”

Section: Introductionmentioning

confidence: 99%

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Peculiar Photoinduced Electron Transfer in Porphyrin–Fullerene Akamptisomers

Stasyuk

Solà

et al. 2019

Chemistry A European J

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Porphyrin–fullerene dyads are promising candidates for organic photovoltaic devices. The electron‐transfer (ET) properties of the molecular devices depend significantly on the mutual position of the donor and acceptor. Recently, a new type of molecular isomerism (akamptisomerism) has been discovered. In the present study, we explore how photoinduced ET can be modulated by passing from one akamptisomer to another. To this aim, four akamptisomers of the quinoxalinoporphyrin–[60]fullerene complex are selected for computational study. The most striking finding is that, depending on the isomer, the porphyrin unit in the dyad can act as either electron donor or electron acceptor. Thus, the stereoisomeric diversity allows one to change the direction of ET between the porphyrin and fullerene moieties. To understand the effect of akamptisomerism on the photoinduced ET processes, a detailed analysis of initial and final states involved in the ET is performed. The computed rate for charge separation is estimated to be in the region of 1–10 ns−1. The formation of a long‐living quinoxalinoporphyrin anion radical species is predicted.

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Section: Resultsmentioning

confidence: 99%

“…Second, the interaction of C 60 and porphyrin stabilizes S a S p compared with S p S a by 6.9 kcal mol −1 . By contrast, the corresponding difluoro derivatives have the same energy …”

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Peculiar Photoinduced Electron Transfer in Porphyrin–Fullerene Akamptisomers

Stasyuk

Solà

et al. 2019

Chemistry A European J

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Stereoisomerization during Molecular Packing

Duan

Manghnani

et al. 2021

Advanced Materials

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Isomerization is an essential chemical process that often evokes dramatic change of chemical, physical, or biological properties. For a long time, isomerization has been known as a transformation that is induced by certain external energy such as light, heat, or mechanical force. Herein, a new isomerization phenomenon is described, which does not require external energy but simply occurs during molecular packing. The proposed isomerization is demonstrated by a series of symmetric donor–acceptor–donor (D–A–D) molecules, the donor of which may adopt two different stereoisomeric forms. Based on the evidence of the asymmetric isomers in crystals, the occurrence of isomerization during molecular packing is proved. Moreover, the unique asymmetric geometry in the solid state favors the restriction of intramolecular motion, resulting in highly efficient organic solids with quantum yields approaching unity.

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Diastereoisomer‐Induced Morphology Tunable Self‐Assembled Organic Microcrystals of Conjugated Molecules for Ultraviolet Laser

Liu

Yang

Xie

et al. 2020

Adv Materials Inter

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Precisely controlling self‐assembly behavior and micro/nanostructure morphology of conjugated materials is significant for constructing optoelectronic devices. Inspired by natural functional materials, molecular stereoisomerism strategy (MSS) is an effective and convenient means to tune their molecular arrangement and macroscopic property of conjugated materials. Herein, a supramolecular chiral difluorenols, 9,9′‐diphenyl‐9H,9′H‐[2,2′‐bifluorene]‐9,9′‐diol (DPFOH), is set as a desirable model to reveal the diastereomeric effects of conjugated molecules toward controlling the micro/nanostructure morphology and optoelectronic behavior for deep‐blue organic laser. Two diastereomers, raceme (rac)‐ and mesomer (meso)‐DPFOH, are obtained and unambiguously elucidated by X‐ray crystallography. It is common sense to observe the slight diastereomeric effects on photophysical properties and electrochemical characteristics in solution or pristine film state for the isotropic phase. Interestingly, as a consequent of the disparate multi‐dimensional intermolecular interaction, rac‐DPFOH molecule can self‐assemble into 1D rod‐shaped but rectangular plate‐shaped microcrystals for meso‐DPFOH. Impressively, rac‐DPFOH microrod presents a well‐defined emission with an excellent ultraviolet microlasing behavior at 398 nm, whereas the 2D microplate of meso‐DPFOH show a broad emission centered at 420 nm without gain processing. Therefore, MSS provides a new approach to design conjugated molecules and tune superstructure morphology for optoelectronic applications.

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A new fundamental type of conformational isomerism

Cited by 47 publications

References 88 publications

Peculiar Photoinduced Electron Transfer in Porphyrin–Fullerene Akamptisomers

Peculiar Photoinduced Electron Transfer in Porphyrin–Fullerene Akamptisomers

Stereoisomerization during Molecular Packing

Diastereoisomer‐Induced Morphology Tunable Self‐Assembled Organic Microcrystals of Conjugated Molecules for Ultraviolet Laser

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