The aim of this review is to give an update on current progress in the synthesis, properties and applications of thiophene-based conjugated systems bearing tetrathiafulvalene (TTF) units. We focus mostly on the synthesis of poly- and oligothiophenes with TTF moieties fused to the thiophene units of the conjugated backbone either directly or via a dithiin ring. The electrochemical behaviour of these materials and structure-property relationships are discussed. The study is directed towards the development of a new type of organic semiconductors based on these hybrid materials for application in organic field effect transistors and solar cells.
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http://dx.doi.org/10.3762/bjoc.11.191 | DOI Listing |
Org Biomol Chem
March 2024
Department of Chemical Science and Engineering, Kobe University, 1-1 Rokkodai, Nada, Kobe 657-8501, Japan.
Nickel-catalyzed syntheses of oligothiophene and polythiophene were carried out with Ni(cod)(dq) (COD: 1,5-cycloctadiene; DQ: duroquinone) as a catalyst precursor. Studies on the ligand exchange of Ni(cod)(dq) revealed that a high temperature was necessary to replace COD and DQ with PPh and N-heterocyclic carbene IPr. A coupling reaction of a metalated 3-hexylthiophene with 2-chloro-3-hexylthiophene employing Ni(cod)(dq) with IPr proceeded with a remarkably reduced amount of homocoupling byproduct.
View Article and Find Full Text PDFJ Mol Model
August 2023
Vocational School of Food, Agriculture and Livestock, University of Bingöl, 12000, Bingöl, Turkey.
Context: Oligothiophenes have long been used as model compounds to understand the chemistry of polythiophenes. Herein, we have some quantum chemical calculations and intra- and inter-molecular interaction calculations of a series of oligothiophenes such as terthiophene, quintetthiophene, sevensthiophene, terthiophene-terthiophene, terthiophene-water, terthiophene-methanol, and terthiophene-chloroform performed by time-dependent density functional theory (TD-DFT), density functional theory (DFT), and Multiwfn: a multifunctional wavefunction analyzer. The UV-vis spectra, HOMO-LUMO energies, NBO analysis, MEP, molecular structures, and electronic properties were computed using DFT/TD-DFT at the level of B3LYP/6-31+ G (d,p) and described.
View Article and Find Full Text PDFJ Mol Graph Model
September 2023
Faculty of Science, Department of Chemistry, Izmir Institute of Technology, 35430, Urla, Izmir, Turkiye. Electronic address:
In this work, molecular dynamics simulations of complexes composed of single strand DNA (ssDNA) sequences and cationic oligothiophenes are performed to understand experimental findings and the sensing ability of polythiophene electrolytes toward ssDNA. The simulation results exhibit no significant structural effect for replacing the cationic amine moiety with imidazole derivative on the side group of the oligomer. Adding a homopurine strand elongates the oligomer backbone; on the contrary, mixing up the homopyrimidine strand causes compression.
View Article and Find Full Text PDFRSC Adv
February 2023
ISIS Neutron and Muon Source, STFC Rutherford Appleton Laboratory Chilton Didcot OX11 0QX UK
We have measured the infrared, Raman and inelastic neutron scattering (INS) spectra of a series of oligothiophenes (bithiophene, terthiophene, quarterthiophene, sexithiophene and octithiophene) and polythiophene, both pristine and after doping with iodine. The spectra of the pristine (. neutral) systems show a rapid convergence towards the spectrum of polythiophene, such that the spectra of sexithiophene and octithiophene are almost indistinguishable from that of polythiophene.
View Article and Find Full Text PDFACS Omega
January 2022
Department of Chemistry, COMSATS University Islamabad, Abbottabad Campus, Abbottabad 22060, Pakistan.
Composite formation with graphene is an effective approach to increase the sensitivity of polythiophene (PT) gas sensors. The interaction mechanism between gaseous analytes and graphene/PT composite systems is still not clear, and density functional theory calculations are used to explore the interaction mechanism between graphene/PT nanoribbon composites (with = 3-9 thiophene units) and gaseous analytes CO, NH, SO, and NO. For the studied analytes, the interaction energy ranges from -44.
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