Solubility and Crystallizability: Facile Access to Functionalized π‐Conjugated Compounds with Chlorendylimide Protecting Groups

Abstract

Functional π-conjugated molecules are relevant for the preparation of new organic electronic materials with improved performance. However, their synthesis is often rendered difficult by their inherently low solubility, and the permanent attachment of solubilizing groups may change the properties of the material. Here, we introduced the chlorendylimidyl moiety as a new temporary protecting group for the straightforward large-scale synthesis of protected quarter-, sexi-, octathiophene, and perylene bisimide diamine and dicarboxylic acid derivatives. The obtained chlorendylimides and chlorendylimidyl active esters were highly soluble in organic solvents, and optical spectroscopy confirmed the low tendency of the compounds to aggregate in solution. At the same time, they could be conveniently purified by recrystallization or precipitation. Single-crystal X-ray structures obtained for most compounds showed supramolecular motifs highlighting the role of the rigid, polychlorinated chlorendyl moieties in their crystallization. The obtained protected diamine and dicarboxylic acid derivatives were easily deprotected and converted into various amide-substituted oligothiophenes and perylene bisimides that are of interest as new functional materials for organic electronic thin film or nanowire devices.

Structure–Property Relationships in Bithiophenes with Hydrogen‐Bonded Substituents

“…Materials : Unless stated otherwise, all materials and solvents for reactions were purchased from commercial suppliers and used without further purification. Methyl 2‐(thiophen‐2‐yl)acetate ( 2 a ), dimethyl 2,2′‐(2,2′‐bithiophene‐5,5′‐diyl)diacetate ( 1 a ), dimethyl 3,3′‐(2,2′‐bithiophene‐5,5′‐diyl)dipropionate ( 1 b ), and methyl 4‐(thiophen‐2‐yl)butanoate ( 2 c ) were prepared following literature procedures [56–58] . α,ω‐Dihexylbithiophene (DHT2) was purchased from Sigma–Aldrich.…”

“…Methyl 2-(thiophen-2-yl)acetate (2a), dimethyl 2,2'-(2,2'-bithiophene-5,5'-diyl)diacetate (1a), dimethyl 3,3'-(2,2'-bithiophene-5,5'-diyl)dipropionate (1b), and methyl 4-(thiophen-2-yl)butanoate (2c)w ere prepared following literature procedures. [56][57][58] a,w-Dihexylbithiophene (DHT2) was purchased from Sigma-Aldrich. Chromatography solvents were purchased as reagent grade and distilled once prior to use.…”

Synthesis and characterization of original [2]rotaxanes including cyclodextrin

“…4). Regarding the formation of amic acid, literature search did not show any sign of opening of the anhydride ring to give the free amic acid [36][37][38][39][40]. Scheme 2 indicates the mechanism for synthesis of [2][succinic dihydrazide]-rota-[β-cyclodextrin] (2).…”

Charge separation in an acceptor–donor–acceptor triad material with a lamellar structure

“…Addition of bromopropane finally yielded the unsymmetric perylene diesters 3a and 3b, respectively. The ester functions were subsequently cleaved in acidic conditions, and the resulting perylene monoanhydrides 4a and 4b were coupled to 2,5'''-bis(2-amino-ethyl)-5,2':5',2'':5'',2'''quaterthiophene 26 in quinoline at 175°C, yielding the desired triads PTP-9 and PTP-19 (Supplementary Figure S1). Moreover, the poly(isobutylene)-substituted perylene bisimide 5 and the quaterthiophene 6 were prepared as reference compounds.…”

“…Moreover, the poly(isobutylene)-substituted perylene bisimide 5 and the quaterthiophene 6 were prepared as reference compounds. 26,27 Molecularly disperse solutions of PTP-9 and PTP-19 in o-dichlorobenzene (c = 25 μmol/L) were obtained at 100°C. The steady-state UV/vis absorption spectra of these solutions at 100°C (Figure 2a) resembled a superposition of the absorption spectra of perylene bisimide 5 and quaterthiophene 6, confirming that no significant electronic coupling occurred between both chromophores.…”