Pawel Zassowski

UV-vis and EPR spectroelectrochemical investigations of triarylamine functionalized arylene bisimides

Four arylene bisimides N-substituted with triarylamine and three bisimides core-functionalized with the same substituent were studied by cyclic voltammetry, UV-vis and EPR spectroelectrochemistry. All the investigated compounds showed ambipolar behaviour manifested by their quasi-reversible reduction to radical anions and quasi-reversible oxidation to radical cations. The presence of stable radical anions and radical cations was confirmed by EPR spectroelectrochemical experiments. Formation of the radical anions resulted in bleaching of the bisimide UV-vis bands with simultaneous hypsochromic shift of the charge transfer (CT) band and appearance of the radical anion peaks, the bands originating from the triarylamine remaining essentially unchanged. Electrochemical generation of radical cations resulted in turn in bleaching of the triarylamine band accompanied by a hypsochromic shift of the CT band and with the appearance of the radical cation bands at higher wavelengths, the bisimide bands remained essentially intact.

A novel donor–acceptor carbazole and benzothiadiazole material for deep red and infrared emitting applications

A novel organic material (C1) with the structure D–π–A–π–D was synthesised and characterised. Carbazole was utilised as the electron donor and benzothiadiazole as the electron acceptor unit. The electrochemical, optical and electronic properties of the synthesised compound were studied. Compound C1 exhibits absorption in the visible and ultraviolet range with a high molar absorption coefficient. A strong solvatochromic effect was observed in its emission spectra. Electrochemical and spectroelectrochemical measurements were performed in order to estimate the properties of the molecule in different redox states. Electron paramagnetic resonance (EPR) measurements indicate the delocalisation of radical cations and radical anions over different moieties. Interpretations of the electrochemical and optical results are supported by DFT calculations. OLEDs based on C1 present efficient emission in red and infrared spectral ranges, with a quantum efficiency of 3.13% and a current efficiency of 6.8 cd A−1. The performance is considerably better than what has been reported for analogous devices, based on other carbazole and benzothiadiazole units.

Electrochemically induced synthesis of poly(2,6-carbazole)

The formation of a poly(2,6-carbazole) derivative during an electrochemical polymerization process is shown. Comparison of 3,5-bis(9-octyl-9H-carbazol-2-yl)pyridine and 3,5-bis(9-octyl-9H-carbazol-3-yl)pyridine by electrochemical and UV-Vis-NIR spectroelectrochemical measurements and DFT (density functional theory) calculation prove the formation of a poly(2,6-carbazole) derivative. Both of the compounds form stable and electroactive conjugated polymers.

Fused H-shaped tetrathiafulvalene–oligothiophenes as charge transport materials for OFETs and OPVs

A series of hybrid tetrathiafulvalene–oligothiophene compounds has been synthesised, where the tetrathiafulvalene unit is fused at each side to an end-capped oligothiophene chain of varying length (terthiophene, quinquithiophene and septithiophene). Each hybrid structure (1–3) has been studied by cyclic voltammetry and triple EPR-UV-Vis-NIR spectroelectrochemistry in the case of the quinquithiophene compound (2). Comparison is made with the corresponding half-units, which lack the fulvalene core and contain just one oligothiophene chain. The highest hole mobility of quinquithiophene–TTF 2 was obtained from field effect transistors (8.61 × 10−3 cm2 V−1 s−1); its surface morphology was characterised by tapping mode atomic force microscopy and a power conversion of 2.5% was achieved from a bulk heterojunction organic solar cell device using PC71BM as the acceptor.

Electrochemistry and In Situ EPR Spectroelectrochemistry of Poly(3,4-ethylenedithiothiophene)

Polymer films of poly(3,4-ethylenedithiothiophene) obtained by electrochemical oxidative polymerisation of the corresponding monomer have been investigated. p-Doping process of the polymer was characterized by in situ EPR spectroelectrochemisty. Compared to its close relative – PEDOT, the polymer features two distinct voltammetric peaks. The results of our studies indicate that both represent faradaic processes and that each manifests generation of charge carriers in the polymer.

Low and high molecular mass dithienopyrrole‐naphthalene bisimide donor‐acceptor compounds: synthesis, electrochemical and spectroelectrochemical behaviour

Two low molecular weight electroactive donor-acceptor-donor (DAD)-type molecules are reported, namely naphthalene bisimide (NBI) symmetrically core-functionalized with dithienopyrrole (NBI-(DTP)2 ) and an asymmetric core-functionalized naphthalene bisimide with dithienopyrrole (DTP) substituent on one side and 2-ethylhexylamine on the other side (NBI-DTP-NHEtHex). Both compounds are characterized by low optical bandgaps (1.52 and 1.65 eV, respectively). NBI-(DTP)2 undergoes oxidative electropolymerization giving the electroactive polymer of ambipolar character. Its two-step reversible reduction and oxidation is corroborated by complementary EPR and UV/Vis-NIR spectroelectrochemical investigations. The polymer turned out to be electrochemically active not only in aprotic solvents but also in aqueous electrolytes, showing a distinct photocathodic current attributed to proton reduction. Additionally, poly(NBI-(DTP)2 ) was successfully tested as a photodiode material.

Unravelling the role of electron–hole pair spin in exciton dissociation in squaraine-based organic solar cells by magneto-photocurrent measurements

A high absorption coefficient and narrow absorption bands in squaraine (SQ) dyes have resulted in rapidly growing interest in them as a donor material in photovoltaic devices. The exciton dissociation process in organic systems proceeds via a multistep mechanism where the electron–hole pairs (charge transfer states) involved in the current generation process determine the recombination losses and subsequently limit the overall performance of organic solar cells. In this work, these basic electronic processes are investigated by magneto-photocurrent measurements (MPC, the photocurrent change induced by the external magnetic field) of SQ:PC60BM bulk-heterojunction solar cells with varying electron acceptor concentrations under magnetic fields up to 9 T and at different temperatures. Under a weak external magnetic field, the change in photocurrent is due to electron and hole (e–h) pairs that experience a modulating hyperfine interaction associated with nuclear (mainly proton) magnetic moment, while in strong magnetic fields the photocurrent is affected by the Δg mechanism with spin dephasing due to different Lande factors of the electron and hole entities (Δg ≈ 10−3). To consistently interpret the amplitudes and lineshapes of the MPC signals at various temperatures, charge carrier hopping in a disordered environment competing with the magnetic dipole spin precession is proposed. The requirements for efficient small-molecular weight organic:fullerene bulk-heterojunction solar cells are briefly discussed.