An effective multipurpose building block for 3D electropolymerisation: 2,2′-Bis(2,2′-bithiophene-5-yl)-3,3′-bithianaphthene

Sannicolò, F.; Rizzo, Simona; Benincori, Tiziana; Kutner, Włodzimierz; Noworyta, Krzysztof; Sobczak, Janusz W.; Bonometti, V.; Falciola, L.; Mussini, Patrizia R.; Pierini, Marco

doi:10.1016/j.electacta.2010.04.070

Cited by 32 publications

(40 citation statements)

References 42 publications

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“…On the contrary, changing the all-C fluorene core with a carbazole core appears to powerfully promote polymerization, albeit with significant differences in the four cases considered : 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65 20 a) both the 3,6 Th-Cbz-Th monomers that have an angular structure (C' 1 and C' 2 ), polymerize faster than the linear 2,7 Th-Cbz-Th monomers (C 1 and C 2 ) at constant cycle number, besides having a significantly lower first oxidation potential, as above accounted for; this feature appears consistent with a recent study of some of us on an intrinsically 3D multithiophene monomer, powerfully enhancing electropolymerization rates thanks to the central angle in the molecule [76]; moreover, the high dihedral angle hampering conjugation should result in more peripherally localized and therefore more reactive radical cations.…”

Section: (Figure 7 Here)supporting

confidence: 75%

Ternary thiophene–X–thiophene semiconductor building blocks (X=fluorene, carbazole, phenothiazine): Modulating electronic properties and electropolymerization ability by tuning the X core

Tacca

Pò

Caldararo

et al. 2011

Electrochimica Acta

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To achieve rationalization criteria for target-oriented molecular design of Th-X-Th (Th = thiophene) semiconductor building blocks, we have carried out an extensive investigation on the effects of the X core (X = fluorene, carbazole or phenothiazine) on the electronic properties and polymerization ability of Th-X-Th monomers and on the electronic and structural properties of the corresponding periodic conducting polymers -(Th-X-Th) n -, obtained by electropolymerization and, for

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Section: (Figure 7 Here)supporting

confidence: 75%

Ternary thiophene–X–thiophene semiconductor building blocks (X=fluorene, carbazole, phenothiazine): Modulating electronic properties and electropolymerization ability by tuning the X core

Tacca

Pò

Caldararo

et al. 2011

Electrochimica Acta

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“…[18] Moreover, 1 a rapidly and regularly oligomerizes, and serves as a 3D promoter building block in copolymerization with monomers endowed with key functional properties which do not undergo electropolymerization easily. Interestingly, the 3,3'-junction of the internal thiophene units, generally considered a defective connection in polyconjugated systems, does play the essential role of granting electronic communication between the two halves of the molecule.…”

mentioning

confidence: 99%

“…The potentiodynamic electrooligomerization of (AE)-1 a [18] and that of the enantiomers develops regularly by potential cycling in dichloromethane, resulting in highly stable films of enhanced conjugation with respect to the monomers. They are constituted of oligomers, from the dimer, the largely prevailing one, to the hexamer (Laser Desorption Ionization, LDI), and exhibit charge-trapping features (see the Supporting Information).…”

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confidence: 99%

Potential‐Driven Chirality Manifestations and Impressive Enantioselectivity by Inherently Chiral Electroactive Organic Films

et al. 2014

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The typical design of chiral electroactive materials involves attaching chiral pendants to an electroactive polyconjugated backbone and generally results in modest chirality manifestations. Discussed herein are electroactive chiral poly-heterocycles, where chirality is not external to the electroactive backbone but inherent to it, and results from a torsion generated by the periodic presence of atropisomeric, conjugatively active biheteroaromatic scaffolds, (3,3'-bithianaphthene). As the stereogenic element coincides with the electroactive one, films of impressive chiroptical activity and outstanding enantiodiscrimination properties are obtained. Moreover, chirality manifestations can be finely and reversibly tuned by the electric potential, as progressive injection of holes forces the two thianaphthene rings to co-planarize to favor delocalization. Such deformations, revealed by CD spectroelectrochemistry, are elastic and reversible, thus suggesting a breathing system.

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“…[2] The preliminary experiments have been carried out on racemic (AE)-1 a. [3] Extraction with THF in a Soxhlet apparatus of the crude reaction product to remove some insoluble iron-containing materials, gives an orange residue (50 % yields in weight), composed of dimers (67 %), trimers (27 %), tetramers (2 %) and pentamers (less than 1 %), on the basis of peak intensities in laser desorption ionization (LDI) mass spectrum (see the Supporting Information section SI 1). High resolution LDI (HR-LDI) experiments show that the molecular weights and the isotopic Scheme 1.…”

mentioning

confidence: 99%

Inherently Chiral Macrocyclic Oligothiophenes: Easily Accessible Electrosensitive Cavities with Outstanding Enantioselection Performances

Sannicolò

Mussini

Benincori

et al. 2014

Chemistry A European J

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Linear conjugated oligothiophenes of variable length and different substitution pattern are ubiquitous in technologically advanced optoelectronic devices, though limitations in application derive from insolubility, scarce processability and chain-end effects. This study describes an easy access to chiral cyclic oligothiophenes constituted by 12 and 18 fully conjugated thiophene units. Chemical oxidation of an "inherently chiral" sexithiophene monomer, synthesized in two steps from commercially available materials, induces the formation of an elliptical dimer and a triangular trimer endowed with electrosensitive cavities of different tunable sizes. Combination of chirality with electroactivity makes these molecules unique in the current oligothiophenes literature. These macrocycles, which are stable and soluble in most organic solvents, show outstanding chiroptical properties, high circularly polarized luminescence effects and an exceptional enantiorecognition ability.We have recently reported the example of a new approach to chiral electroactive oligothiophenes, consisting in the electrooligomerization of monomers (R)-1 a and (S)-1 a in which chirality results from an internal torsion in the conjugated backbone (from here the appellative of inherently chiral monomers).[1] According to this design, the same conjugated system responsible for the electro-optical properties of these materials is also responsible for molecular chirality, implying that electrochemical, chiroptical and enantiorecognition properties are strictly interdependent (Scheme 1).The conducting films resulting from electro-oxidation of enantiopure (R)-1 a and (S)-1 a, constitute oligomers from the dimer (largely prevailing) to the pentamer (present in traces). They display impressive chiroptical activity, reversible potential-driven variations of the circular dichroism (CD) signal and outstanding enantioselection ability towards a chiral ferrocenylamine selected as an electrochemical probe.Here we report the results obtained when performing the chemical oxidation of racemic 1 a and its enantiopure antipodes with FeCl 3 excess, in CHCl 3 solution, under stirring, at RT, according to a procedure currently employed for preparing polythiophenes from electron-rich monomers when regioselectivity problems are not involved. [2] The preliminary experiments have been carried out on racemic (AE)-1 a.[3] Extraction with THF in a Soxhlet apparatus of the crude reaction product to remove some insoluble iron-containing materials, gives an orange residue (50 % yields in weight), composed of dimers (67 %), trimers (27 %), tetramers (2 %) and pentamers (less than 1 %), on the basis of peak intensities in laser desorption ionization (LDI) mass spectrum (see the Supporting Information section SI 1). High resolution LDI (HR-LDI) experiments show that the molecular weights and the isotopic Scheme 1. The inherently chiral enantiomeric monomers employed in the present research.[a] Prof.

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An effective multipurpose building block for 3D electropolymerisation: 2,2′-Bis(2,2′-bithiophene-5-yl)-3,3′-bithianaphthene

Cited by 32 publications

References 42 publications

Ternary thiophene–X–thiophene semiconductor building blocks (X=fluorene, carbazole, phenothiazine): Modulating electronic properties and electropolymerization ability by tuning the X core

Ternary thiophene–X–thiophene semiconductor building blocks (X=fluorene, carbazole, phenothiazine): Modulating electronic properties and electropolymerization ability by tuning the X core

Potential‐Driven Chirality Manifestations and Impressive Enantioselectivity by Inherently Chiral Electroactive Organic Films

Inherently Chiral Macrocyclic Oligothiophenes: Easily Accessible Electrosensitive Cavities with Outstanding Enantioselection Performances

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