Functionalised tetrathiafulvalenes in supramolecular chemistry

Using a range of functionalised tetrathiafulvalene (TTF) derivatives, developed at Durham, the first examples of covalently linked TTF-ferrocene systems have been prepared. The redox properties of these molecules, as studied by cyclic voltammetry, provide evidence that these species are efficient π-electron donors. Highly reactive 1,3-dithiole Wittig and Wittig-Homer reagents have been used in the synthesis of complex mixed redox-active systems containing ferrocenyl units. A series of [3]- and [4]-dendralenes has also been developed from this synthetic methodology. Cyclic voltammetry shows that tri- and tetracationic states can be achieved with these systems at relatively low potentials. The potential for vinyl-TTF compounds to undergo [4+2] cycloaddition has been investigated for the first time. The peripheral C=C unit of TTF, together with the adjacent vinylic substituent, is able to act as the diene functionality in Diels-Alder reactions. Remarkably, the π-delocalisation within the TTF moieties is readily disrupted by the addition of strong dienophiles. The reactivity of lithiated TTF towards aldehydes and ketones has established an array of hydroxy-functionalised TTF, bis-TTF and TTF-ferrocene derivatives. The conducting and magnetic properties of the chloranil charge transfer salt of one of these species is also reported

Scale-up chemical synthesis of thermally-activated delayed fluorescence emitters based on the dibenzothiophene-S,S-dioxide core

We report a procedure to linearly scale-up the synthesis of 2,8-bis(3,6-di-tert-butyl-9H-carbazol-9-yl)dibenzothiophene-S,S-dioxide (compound 4) and 2,8-bis(10H-phenothiazin-10-yl)dibenzothiophene-S,S-dioxide (compound 5) using Buchwald-Hartwig cross-coupling reaction conditions. In addition, we demonstrate a scaled-up synthesis of all non-commercially available starting materials that are required for the amination crosscoupling reaction. In the present article, we provide the detailed synthetic procedures for all of the described compounds, alongside their spectral characterization. This work shows the possibility to produce organic molecules for optoelectronic applications on a large scale, which facilitates their implementation into real world devices

Polythiophene and oligothiophene systems modified by TTF electroactive units for organic electronics

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

Polyterthiophenes incorporating 3,4-difluorothiophene units : application in organic field-effect transistors

Two terthiophenes bearing core fluorinated thienyl units have been synthesised as potential semiconductor materials for organic field-effect transistors. Polymerisation of these compounds has been achieved using conventional iron(III) chloride oxidative coupling methods and by electrochemical oxidation. Characterisation of the fluorinated materials has been achieved by absorption spectroscopy and cyclic voltammetry. A soluble hexyl-functionalised polymer (poly8b) was used in an OFET device; hole mobilities were measured up to 3 × 10−3 cm2 · V−1 · s−1, and the device had an on/off ratio of 105 and a turn-on voltage of +4 V

LED pumped polymer laser sensor for explosives

The authors would like to acknowledge financial support for this research from the EPSRC HYPIX project (grant number EP/ F059922/1 and EP/F05999X/1), and the TIRAMISU project, funded by the European Commission's Seventh Framework Programme (FP7/2007-2013) under grant agreement n° 284747.A very compact explosive vapor sensor is demonstrated based on a distributed feedback polymer laser pumped by a commercial InGaN light-emitting diode. The laser shows a two-stage turn on of the laser emission, for pulsed drive currents above 15.7 A. The 'double-threshold' phenomenon is attributed to the slow rise of the ∼30 ns duration LED pump pulses. The laser emits a 533 nm pulsed output beam of ∼10 ns duration perpendicular to the polymer film. When exposed to nitroaromatic model explosive vapors at ∼8 ppb concentration, the laser shows a 46% change in the surface-emitted output under optimized LED excitation. A very compact explosive vapor sensor is demonstrated based on a distributed feedback polymer laser pumped by a commercial InGaN light-emitting diode. The laser shows a two-stage turn on of the laser emission, for pulsed drive currents above 15.7 A. The 'double-threshold' phenomenon is attributed to the slow rise of the ∼30 ns duration LED pump pulses. The laser emits a 533 nm pulsed output beam of ∼10 ns duration perpendicular to the polymer film. When exposed to nitroaromatic model explosive vapors at ∼8 ppb concentration, the laser shows a 46% change in the surface-emitted output under optimized LED excitation.Publisher PDFPeer reviewe

BODIPY-based conjugated polymers for broadband light sensing and harvesting applications

The synthesis of novel low band-gap polymers has significantly improved light sensing and harvesting in polymer-fullerene devices. Here the synthesis of two low band-gap polymers based on the 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene core (BODIPY), and either bis(3,4-ethylenedioxythiophene) (bis-EDOT) or its all-sulfur analogue bis(3,4-ethylenedithiathiophene) (bis-EDTT) are described. The polymers demonstrate ambipolar charge transport and are shown to be suitable for broadband light sensing and solar energy harvesting in solution-processable polymer-fullerene devices

The damaging effects of the acidity in PEDOT:PSS on semiconductor device performance and solutions based on non-acidic alternatives

Poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate), PEDOT:PSS, has been widely used as an effective hole transporting material in many different organic semiconductor devices for well over a decade. However, despite having many strong features which make this material such a popular hole transport/injection layer, PEDOT:PSS is well-known to cause degradation in devices and limit their stability due to the acidity of the PSS chain. This review focusses on the attempts that have been made to combat this problem, with different strategies explored, including the development of neutral analogues, use of alternative materials and the introduction of barrier layers to prevent degradation of the electrode. Since solution-processing is a key advantage of using PEDOT:PSS, we concentrate on analogous materials that can also be solution-processed, with particular attention on whether orthogonal processing can be retained. We intend this work to be a useful guide for researchers considering enhanced device lifetimes, an important parameter when considering organic semiconductor devices for commercialisation

Acceptor–donor–acceptor small molecules based on derivatives of 3,4-ethylenedioxythiophene for solution processed organic solar cells

Three simple semiconducting acceptor–donor–acceptor (A–D–A) small molecules based on an electron-rich (3,4-ethylenedioxythiophene) EDOT central core have been synthesised (DIN-2TE, DRH-2TE, DECA-2TE) and characterised. Organic photovoltaic (OPV) devices incorporating these materials have been prepared and evaluated. The physical properties of the molecules were characterised by TGA, DSC, UV/vis spectroscopy and cyclic voltammetry. The optical HOMO–LUMO energy gaps of the molecules in the solid state were in the range 1.57–1.82 eV, and in solution 1.88–2.04 eV. Electrochemical HOMO–LUMO energy gaps determined by cyclic voltammetry were found to be in the range 1.97–2.31 eV. The addition of 1% 1,8-diiodooctane (DIO) to photoactive blends of the A–D–A molecules and PC71BM more than doubled the power conversion efficiency (PCE) in the case of DRH-2TE:PC71BM devices to 1.36%

Tetrathiafulvalene chemistry

Tetrathiafulvalene (TTF) is a fascinating system: it is quite rare to find a synthetic molecule endowed with such a simple architecture that is capable of concentrating intense interest from various communities of chemists! This modest-sized molecule which consists of only 14 atoms, was synthesized in the early nineteen seventies [1-3] and since then has proved to be exceptionally popular in various fields of chemistry

Novel polymer materials for low-cost nitro vapor detection sensors

Current commercial sensors for explosive vapours are high cost bulky equipment not amenable to mass production and thus prevents their mass deployment within society. Our research objective is to create compact sensors that are not only portable but of such low cost that they can be installed in buildings in the same way as smoke detectors. We have developed novel polymers whose properties have been tailored to give them a higher affinity to target nitro group (NO2) bearing molecules associated with explosives. The polymers have been grown electrochemically onto miniature interdigitated electrode platforms yielding miniature sensors. Novel porous polymers based sensors are demonstrated which yield a detection level of 200 ppb of nitro vapours and can be manufactured at low-unit-cost