105125-00-6Relevant articles and documents
Improved synthesis of a terthiophene-based monomeric ligand that forms a highly active polymer for the carbon dioxide reduction
Quagliotto, Pierluigi,Prosperini, Simona,Viscardi, Guido
, p. 472 - 478 (2017/08/29)
Background: The carbon-dioxide reduction to obtain important chemicals such as fuels is a topic of high current interest. Recently, monomeric thiophenes and terthiophenes linked to a bipyridine ligand were designed and their polymeric films achieved very high turnover numbers during electrocatalytic CO2 reduction. In this paper we improved the protocol to access the ligand that shows the best performances, in view of opening the way to a general method to obtain side-functionalized terthiophenes. Methods: Several reactions were attempted to improve the synthetic pathway. Different approaches were attempted to convert the 3-bromothiophene into its 3-iodo analog and to brominate it to obtain the 2,5-dibromo-3-iodothiophene. The synthetic pathway was completed by using Pd-catalyzed crosscoupling reactions such as Sonogashira and Suzuki. The removal of a trimethylsilyl protection was attempted by common methods. However, with the use of a one-pot reaction, both the alkyne deprotection and the final Sonogashira coupling were performed as the key point of the pathway to obtain the final product. Results: The key intermediate 2,5-dibromo-3-iodothiophene was obtained by a CuI assisted electrophilic aromatic substitution, followed by a bromination with NBS in ethyl acetate. This compound was reacted with TMS-acetylene to obtain the ((2,5-dibromothiophen-3-yl)ethynyl)trimethylsilane which, by a Suzuki reaction, afforded the ([2,2':5',2''-terthiophen]-3'-ylethynyl)trimethylsilane. Using a onepot reaction for the last step, the deprotection of the TMS-protected alkyne and its coupling with 4- bromo-2,2'-bipyridine was accomplished easily. A final 52% yield was achieved over 5 steps. Conclusion: The ligand 4-([2,2':5',2''-terthiophen]-3'-ylethynyl)-2,2'-bipyridine was prepared in a 52% yield, over 5 steps, improving the previous protocol (17% yield over 4 steps). The rhenium complex of this ligand is still under study for CO2 reduction. This novel protocol can be used to produce a series of analog terthiophene monomers bearing side-attached ligands.
Conjugated oligomers with thiophene and indole moieties: Synthesis, photoluminescence and electrochromic performances
Dong, Ben,Li, Baoyan,Cao, Yi,Meng, Xinlei,Yan, Han,Ge, Shusheng,Lu, Yun
supporting information, p. 35 - 42 (2016/12/23)
Two series of thiophene oligomers and terthiophene oligomers consisting of both thiophene and indole moieties have been synthesized. They have same excitation-dependent photoluminescence characteristics, but different bandgaps and absorption behaviors, which relates to the number and denseness of indoles in the conjugated oligomers and the length of alkyl chains on indole moiety due to varied the π-π stacking interaction of conjugated structures in the as-prepared oligomers. A simple electrochromic device based on such a conjugated oligomer displays a novel four-color electrochromism from red to yellow, green and puce with the increased potential and possesses good environmental and redox stability. Such conjugated oligomer also exhibits high sensitivity and selectivity for Zn2+detection.
Conducting cell scaffold - Poly(3'-aminomethyl-2,2':5',2″-terthiophene)
Jeong, Euh-Duck,Whang, Jae Young,Lee, Joo-Woon
, p. 1114 - 1119 (2015/08/11)
Electroactive biomaterials such as polythiophene (PT) are highly attractive scaffolds for tissue engineering applications. The introduction of reactive functionalities into the PT backbone structure is desired to enhance the biomaterial-tissue interface for desired tissue responses. Here, we present amino-functionalized conductive polyterthiophene, poly(3'-aminomethyl-2,2':5',2″-terthiophene) (PTTh-NH2), which successfully demonstrates the potential to influence cellular activity. The chemical structure of monomeric 3'-aminomethyl-2,2':5',2″-terthiophene was confirmed by MS and the polymer characteristics of PTTh-NH2 were determined by AFM, XPS, profilometer and four-point probe. In vitro cell viability study with human umbilical vascular endothelial cells (HUVECs) indicates that the primary amine functionality grafted into polythiophene (PT) backbone improve the cell adhesion and proliferation compared to negative (-) control conventional PT. Thus, PTTh-NH2 could be useful in developing PT composites for various biomedical applications.
