Carbo-cyclohexadienes vs. carbo-benzenes: structure and conjugative properties

Rives, Arnaud; Baglai, Iaroslav; Barthes, Cécile; Maraval, Valérie; Saffon‐Merceron, Nathalie; Saquet, Alix; Voitenko, Zoia; Volovenko, Yulian M.; Chauvin, Rémi

doi:10.1039/c4sc02742f

Cited by 13 publications

(11 citation statements)

References 37 publications

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“…It is also completely different from the two-band profile of the conjugated isomer 1Fb [5]. The hypsochromic shift of the  max value of 6 (418 nm) with respect to 9 (453 nm) is attributed to the withdrawing effect of the CF 3 groups of 6.…”

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confidence: 72%

“…The carbo-mers of 1,3-cyclohexadienes 1 and 1F, isolated as cis/trans diastereoisomeric mixtures, were found to be stable chromophores, some of them exhibiting the rare property of dichromism in solution [1,5,7].…”

Section: Methodsmentioning

confidence: 99%

“…Since then, a series of bis-trifluoromethylated conjugated carbo-1,3-cyclohexadienes 1F was developed on the basis of a synthesis procedure involving bis-trifluoromethylated [6]pericyclynic precursors of type 2F (Scheme 2) [5].…”

Section: Introductionmentioning

confidence: 99%

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First example of ring carbomer of 1,4-cyclohexadiene

et al. 2015

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While a series of carbo-mers of 1,3-cyclohexadienes was reported through the use of a specifically developed synthetic strategy, no example of their 1,4-regioisomers was known. Inspired by the methodology elaborated for the preparation of the 1,3-isomers, the synthesis of the first example of carbo-mer of 1,4-cyclohexadiene is presented. Comparison of physico-chemical properties of this first representative with those of the recently described 1,4-regioisomer, especially UV-vis absorption properties, is also addressed.

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confidence: 72%

Section: Methodsmentioning

confidence: 99%

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First example of ring carbomer of 1,4-cyclohexadiene

et al. 2015

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“…The synthetic strategies previously developed for the preparation of related bistrifluoromethylated carbo-cyclohexadienes [1,5] proved however not applicable to the preparation of 6. Recent progress calling for alternative strategies towards this challenging target are reported hereafter.…”

Section: Scheme 1 Synthesis Of Carbo-cyclohexadienes 1 and 1fmentioning

confidence: 99%

“…After the first example of carbo-cyclohexadiene 1 [1,2], a substituted 1,3-cyclohexadiene isolated as a side product of the incomplete reductive aromatization of the hexaoxy [6]pericyclyne 2 [3] to the paradianisyl-carbo-benzene 3 [1,4], a series of 1,10-diversely substituted carbo-cyclohexadienes 1F was very recently accessed through a specific design [5]. This strategy is based on the introduction of trifluoromethyl substituents at two adjacent vertices of [6]pericyclynic precursors 2F, thus preventing the formation of one of the three butatriene moieties in the corresponding carbo-benzenes during reductive treatment with SnCl 2 /HCl (Scheme 1).…”

Section: Introductionmentioning

confidence: 99%

En route to a dianilinyl-substituted carbo-cyclohexadiene with promising electrical properties

et al. 2015

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The macro-aromatic carbo-benzene core para-disubstituted by 4-anilinyl groups is known to be an efficient single-molecule conductor, exhibiting a conductance of 106 nS measured by the scanning tunneling microscopy-break junction technique. The linear carbo-butadiene analogue bearing the same anilinyl substituents was found to be less efficient, with a conductance of 2.7 nS. The reason of this difference could be elucidated through the study of the charge transport properties of a cyclically locked carbo-butadiene core in a carbo-cyclohexadiene derivative. In this paper, advances in the synthesis of this challenging dianilinyl-substituted carbo-cyclohexadiene are presented.

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Difluorenyl carbo‐Benzenes: Synthesis, Electronic Structure, and Two‐Photon Absorption Properties of Hydrocarbon Quadrupolar Chromophores

Baglai

Anda-Villa

Barba-Barba

et al. 2015

Chemistry A European J

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The synthesis, crystal and electronic structures, and one- and two-photon absorption properties of two quadrupolar fluorenyl-substituted tetraphenyl carbo-benzenes are described. These all-hydrocarbon chromophores, differing in the nature of the linkers between the fluorenyl substituents and the carbo-benzene core (C-C bonds for 3 a, C-C=C-C expanders for 3 b), exhibit quasi-superimposable one-photon absorption (1PA) spectra but different two-photon absorption (2PA) cross-sections σ2PA. Z-scan measurements (under NIR femtosecond excitation) indeed showed that the C≡C expansion results in an approximately twofold increase in the σ2PA value, from 336 to 656 GM (1 GM = 10(-50) cm(4) s molecule(-1) photon(-1)) at λ = 800 nm. The first excited states of Au and Ag symmetry accounting for 1PA and 2PA, respectively, were calculated at the TDDFT level of theory and used for sum-over-state estimations of σ2PA(λi), in which λi = 2 hc/Ei, h is Planck's constant, c is the speed of light, and Ei is the energy of the 2PA-allowed transition. The calculated σ2PA values of 227 GM at 687 nm for 3 a and 349 GM at 708 nm for 3 b are in agreement with the Z-scan results.

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Carbo-cyclohexadienes vs. carbo-benzenes: structure and conjugative properties

Abstract: Stable dichromic carbo-cyclohexadiene chromophores are synthesised, selectively with respect to the corresponding carbo-benzenes, by fluorine “chemical locking”.

Cited by 13 publications

References 37 publications

First example of ring carbomer of 1,4-cyclohexadiene

First example of ring carbomer of 1,4-cyclohexadiene

En route to a dianilinyl-substituted carbo-cyclohexadiene with promising electrical properties

Difluorenyl carbo‐Benzenes: Synthesis, Electronic Structure, and Two‐Photon Absorption Properties of Hydrocarbon Quadrupolar Chromophores

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