Synthesis of unsymmetrical benzotrichalcogenophenes by N-heterocyclic carbene–palladium-catalyzed intramolecular direct C3-arylation of chalcogenophenes

Chen, Shi Yen; Pao, Yu Chieh; Sahoo, Santosh Kumar; Huang, Wen; Lai, Yinchieh; Cheng, Yen‐Ju

doi:10.1039/c7cc08852c

Cited by 15 publications

(7 citation statements)

References 32 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…In this study, we wish to report the facile synthesis of two a -BTT- and a -BTS-based donor–acceptor copolymers. a -BTT and a -BTS were used as donor monomers to copolymerize with diketopyrrolopyrrole (DPP) , -based acceptor monomers, resulting in two conjugated PBTTDPP and PBTSDPP copolymers. The chalcogen effect on molecular packing and charge transport of the polymers in thin films will be revealed.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of Asymmetric Benzotrithiophene/Benzotriselenophene Building Blocks and Their Donor–Acceptor Copolymers: Chalcogen Effect on Face-on/Edge-on Orientations and Charge Transport

Huang,

Pao,

Chen

et al. 2023

Macromolecules

Self Cite

View full text Add to dashboard Cite

Two asymmetric 5-octadecanyl benzotrithiophene (BTT) and benzotriselenophene (BTS) were designed and synthesized through a key step of palladium-catalyzed intramolecular C–H arylation. The two-dimensional stannylated BTT and BTS monomers were then polymerized with a DPP comonomer by Stille coupling to afford two new donor–acceptor polymers, PBTTDPP and PBTSDPP. With the chalcogen effect of selenium, PBTSDPP exhibited a higher-lying HOMO level and a more red-shifted absorption than the corresponding PBTTDPP. The crystalline domains of both PBTTDPP and PBTSDPP were analyzed via GIWAXS measurements, revealing perpendicular π–π stacking of the main-chain backbone and lamellar stacking of side-chain interdigitation. The dimensions of the π–π stacking and lamellar stacking of the crystalline domains were estimated by calculating their corresponding correlation lengths (L c). We discovered that the ratio between the correlation lengths of lamellar stacking (L l) and π–π stacking (L π), denoted as (R L), plays a crucial role in determining the edge-on/face-on polymer orientations of substrates. PBTTDPP, with a larger R L of 2.56, predominantly exhibits a face-on orientation, while PBTSDPP, which has a stronger π–π interaction due to Se inclusion, leads to a smaller R L of 1.36, preferring an edge-on orientation. After thermal annealing at 210 °C for 10 min, PBTSDPP forms higher-order crystalline domains, increasing its mobility from 0.04 to 0.17 cm2 V–1 s–1. Despite its face-on orientation, the pristine PBTTDPP, with a higher molecular weight, exhibits the best mobility of 0.61 cm2 V–1 s–1 due to efficient intrachain charge transport and good connectivity between different nanodomains. However, thermal annealing of PBTTDPP leads to a decrease in π–π stacking distance from 3.67 to 3.41 Å, facilitating charge transport via face-on π-stacking hopping perpendicular to the source-to-drain direction. Consequently, the mobility of annealed PBTTDPP is reduced to 0.18 cm2 V–1 s–1. This work demonstrates that the use of benzotrichalcogenophenes in the polymer backbone can fine-tune intermolecular interactions, controlling the orientations in crystalline nanodomains that ultimately determine the charge transport properties.

show abstract

Section: Introductionmentioning

confidence: 99%

Synthesis of Asymmetric Benzotrithiophene/Benzotriselenophene Building Blocks and Their Donor–Acceptor Copolymers: Chalcogen Effect on Face-on/Edge-on Orientations and Charge Transport

Huang,

Pao,

Chen

et al. 2023

Macromolecules

Self Cite

View full text Add to dashboard Cite

show abstract

“…Related π-extended benzotrichalcogenophenes, such as A and B in Chart , are planar electron-rich heteroacenes that have efficient light-absorbing abilities and can form supramolecular assemblies, leading to excellent charge transport properties . Of substantial relevance to this study, Cheng and co-workers prepared the unsymmetric tellura(benzo)bithiophenes ( B , Chart ) via Pd-catalyzed intramolecular arylation; however, the optoelectronic properties of these novel species were not explored in detail . Moreover, a series of fluorescent phospho(benzo)bithiophene isomers with light absorption extending into the near-IR region were reported ( C – E , Chart ).…”

Section: Introductionmentioning

confidence: 99%

“…9 Of substantial relevance to this study, Cheng and co-workers prepared the unsymmetric tellura(benzo)bithiophenes (B, Chart 1) via Pd-catalyzed intramolecular arylation; however, the optoelectronic properties of these novel species were not explored in detail. 10 Moreover, a series of fluorescent phospho(benzo)bithiophene isomers with light absorption extending into the near-IR region were reported (C−E, Chart 1). 11 Lastly, telluraporphyrins 12 and tellurasumanenes 6m,13 represent interesting Te-based heteroacenes that have appeared in the literature recently.…”

Section: ■ Introductionmentioning

confidence: 99%

Tellura(benzo)bithiophenes: Synthesis, Oligomerization, and Phosphorescence

2021

View full text Add to dashboard Cite

A series of planar π-extended Te-containing heteroacenes, termed tellura(benzo)bithiophenes, were synthesized. This new structural class of heterocycle features a tellurophene ring fused to a benzobithiophene unit with aromatic side groups (either −C 6 H 4 i Pr or −C 6 H 4 OCH 3 ) positioned at the 2-and 5-positions of the tellurophene moiety. Although attempts to enhance molecular rigidity and extend ring-framework πdelocalization in a cumenyl (−C 6 H 4 i Pr)-capped tellura(benzo)bithiophene led to oxidation (and Te−C bond scission) to form a diene−one, the formation of an oligomeric tellura(benzo)bithiophene was possible via Kumada catalyst-transfer polycondensation (KCTP). Furthermore, one tellura(benzo)bithiophene derivative exhibits orange-red phosphorescence at room temperature in air when incorporated into a poly(methyl methacrylate) host; accompanying TD-DFT computations provided insight into a potential mechanism for the observed phosphorescence.

show abstract

“…Selenophene derivatives have also been used as ligands in coordination chemistry [91][92][93][94][95][96][97]. After a pre-activation with a halide or an organometallic (B, Li, Mg, Sn or Zn), these compounds can be employed as reagents in the formation of new C-C [98][99][100][101][102][103][104][105][106][107], C-N [108][109][110] and C-S [111] bonds under Pd or Cu catalysis, through Heck, Stille, Negish, Kumada, Suzuki and Sonogashira coupling reactions. In recent years, unactivated selenophenes have been used as reagents in several synthetic transformations by palladium-catalyzed direct C-H bond activation [112][113][114][115][116].…”

Section: Introductionmentioning

confidence: 99%

Recent Advances in the Synthesis of Selenophenes and Their Derivatives

et al. 2020

View full text Add to dashboard Cite

The selenophene derivatives are an important class of selenium-based heterocyclics. These compounds play an important role in prospecting new drugs, as well as in the development of new light-emitting materials. During the last years, several methods have been emerging to access the selenophene scaffold, employing a diversity of cyclization-based synthetic strategies, involving specific reaction partners and particularities. This review presents a comprehensive discussion on the recent advances in the synthesis of selenophene-based compounds, starting from different precursors, highlighting the main differences, the advantages, and limitations among them.

show abstract

Synthesis of unsymmetrical benzotrichalcogenophenes by N-heterocyclic carbene–palladium-catalyzed intramolecular direct C3-arylation of chalcogenophenes

Cited by 15 publications

References 32 publications

Synthesis of Asymmetric Benzotrithiophene/Benzotriselenophene Building Blocks and Their Donor–Acceptor Copolymers: Chalcogen Effect on Face-on/Edge-on Orientations and Charge Transport

Synthesis of Asymmetric Benzotrithiophene/Benzotriselenophene Building Blocks and Their Donor–Acceptor Copolymers: Chalcogen Effect on Face-on/Edge-on Orientations and Charge Transport

Tellura(benzo)bithiophenes: Synthesis, Oligomerization, and Phosphorescence

Recent Advances in the Synthesis of Selenophenes and Their Derivatives

Contact Info

Product

Resources

About