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Dimer and trimer analogues of Spiro-OMeTAD are porous hole transport materials with improved conductivity compared to the parent material and give higher power conversion efficiencies in perovskite solar cells.

Control of the delayed emission of organic compounds is an important factor in the development of new display technology and for the emerging use of organic emitters in sensing and fluorescence microscopy. In particular, there is a need to understand how the phenomena of room-temperature phosphorescence and thermally activated delayed fluorescence intersect. Here, we show that delayed fluorescence can be activated in room temperature phosphorescence emitters by quaternising the sp2-hybridised heterocyclic nitrogens. Furthermore by judicious positioning of a carbazole donor in the meta- or para- position with respect to the ring nitrogen atom, structural and sterical influences combine to tune the origins of the delayed fluorescence from triplet–triplet annihilation to thermally activated delayed fluorescence. Crucially, the quaternisation of nitrogen provides us with the means to fine tune singlet and triplet states in a predictable manner, uncover the intersection between phosphorescence and delayed fluorescence and tip the balance in favour of delayed fluorescence.

SFX-MeOTAD [2,2′,7,7′-Tetrakis(N,N-di(4-methoxyphenyl)amino)-spiro-(fluorene-9,9′-xanthene)] (also known as X60) has emerged as a cost-effective alternative to the ubiquitous, but excessively-expensive, spiro-MeOTAD hole transport material (HTM) in perovskite solar cells. Using its pre-oxidised dicationic salt, SFX-(TFSI)2, a controlled concentration dependent conductivity tuning of this HTM without the requirement of air (oxygen) exposure is carried out. This study details the modifications in optical and electrical properties of this low cost HTM as a function of concentration of the dicationic salt (0-100 mol %) using UV-Vis absorption and electrical conductivity measurements. X-ray absorption and photoelectron spectroscopic investigations have been carried out to elucidate the role of the dicationic salt on the enhanced electronic properties of SFX-MeOTAD. By incorporating the dicationic SFX-(TFSI)2 it was shown that the conductivity of SFX-MeOTAD increased by 4 orders of magnitude from 2.55 × 10-8 S cm-1 to 9.4 × 10-4 S cm-1 using an optimal dopant concentration of 20.5 mol %. The degree of oxidation of SFX-MeOTAD was determined through UV-Vis absorption and consolidated by the computational calculations. XPS study reveal that doping SFX-MeOTAD with SFX(TFSI)2 results not only in oxidation of the HTM but also leads to variation in the local chemistry around carbon and nitrogen which directly influence the conductivity of the doped films. NEXAFS studies indicates that doping enhances the aromatic nature of the molecule initially but increasing the dopant concentration further affects the aromaticity and possibly the π stacking, similar to the trend seen in dopant concentration dependent conductivity of the SFX-MeOTAD films. These findings have implications on the choice of dopant concentration and counterions more generally for triarylamine based HTMs.

GC acknowledges the EPSRC for funding (EP/E036244/1). JMS acknowledges the Coordenação de Aperfeiçoamento de Pessoal de Nível Superior – Brasil (CAPES) – Finance Code 001 for PhD funding. JMS also acknowledges Dr Nor Basid Adiwibawa Prasetya for helpful advice. Dr L. K. Jagadamma acknowledges support from a Marie Skłodowska-Curie Individual Fellowship (European Commission) (MCIF: No. 745776). Thiophene-based semiconductors are amongst the most successful materials in organic electronics. In this contribution, we present the synthesis and characterisation of two thiophene-based macrocycles as well as their evaluation in organic-electronic devices. McT-1 is composed of ten thiophene moieties, whereas in McT-2, four additional electron-deficient benzothiadiazole moieties are incorporated to form a donor–acceptor (D–A) π-system. Red-shifted and broadened absorption spectra as well as more positive redox potentials are observed in McT-2, whereas McT-1 displays a sharper absorption band with a higher extinction coefficient. Macrocycle McT-1 shows emission in the yellow region whereas McT-2 displays emission in the red wavelength region. DFT calculations predict the macrocycles to comprise of mainly the E,E isomers with a near-planar structure, which is further supported by the single crystal X-ray structure for McT-1. Their charge transporting properties are determined by fabricating thin-film OFETs. The photovoltaic properties of McT-1 and McT-2 are also investigated by fabricating bulk heterojunction (BHJ) devices and their potential as photodetectors has been evaluated. Publisher PDF

Authors thank the EPSRC for funding under grants EP/L012200/1 and EP/L012294/1. A new dual-chain oligothiophene-based organic semiconductor, EH-5T-TTC, is presented. The molecule contains two conjugated chains linked by a fused tetrathiocin core. X-ray crystallography reveals a boat conformation within the 8-membered sulfur heterocycle core and extensive π–π and intermolecular sulfur–sulfur interactions in the bulk, leading to a 2-dimensional structure. This unusual molecule has been studied as a ternary component in organic solar cell blends containing the electron donor PTB7-Th and both fullerene (PC71BM) and non-fullerene acceptors ITIC and EH-IDTBR. By incorporating EH-5T-TTC as a ternary component, the power conversion efficiency of the binary blends containing non-fullerene acceptor increases by 17% (from 7.8% to 9.2%) and by 85% for the binary blend with fullerene acceptor (from 3.3% to 6.3%). Detailed characterisation of the ternary blend systems implies that the ternary small molecule EH-5T-TTC functions differently in polymer:fullerene and polymer:non-fullerene blends and has dual functions of morphology modification and complementary spectral absorption. Publisher PDF

4-(9'-Hexylcarbazol-3'-yl)benzaldehyde (Cz-Ph-CHO: 4 ) and 4-(9'-hexylcarbazol-3'- yl)benzylidenemalononitrile (Cz-Ph-CN: 5 ) were synthesised with the structure of D-pi-A,where carbazole, phenylene and formyl/dicyanovinyl groups act as electron donor (D), pi-spacer (pi) and electron acceptor (A) units, respectively. The thermal, electrochemical, optical and intramolecular charge transfer (ICT) properties of compounds 4 and 5 were investigated. Compounds 4 and 5 , in particular their ICT behaviour, were also compared with the closely related structure, 2-(9'-hexylcarbazol-3'-yl)-5-pyridinecarbaldehyde (Cz-Py-CHO: 7 ). For the purpose of tuning chemical structure to obtain targeted properties, electrochemical data and absorption and emission measurements suggest that the dicyanovinyl unit in compound 5 is a better acceptor than formyl in compound 4, and that pyridine in compound 7 is a better pi-spacer than benzene in compound 4 , in exerting ICT characteristics such as fluorosolvatochromism and Stokes shifts. (C) 2021 Elsevier B.V. All rights reserved. Scientific and Technological Research Council of Turkey (TUBITAK)Turkiye Bilimsel ve Teknolojik Arastirma Kurumu (TUBITAK); University of Glasgow; EPSRC ECR Capital Award SchemeUK Research & Innovation (UKRI)Engineering & Physical Sciences Research Council (EPSRC) [EP/S017984/1] Dr. Ahmet Battal thanks the Scientific and Technological Research Council of Turkey (TUBITAK) for 2219-International Postdoctoral Research Fellowship Programme for Turkish Citizens. Dr William Peveler acknowledges the University of Glasgow for an LKAS Scholarship and the EPSRC ECR Capital Award Scheme (EP/S017984/1) for the Duetta instrument.

To rival the performance of modern integrated circuits, single-molecule devices must be designed to exhibit extremely nonlinear current–voltage (I–V) characteristics1,2,3,4. A common approach is to design molecular backbones where destructive quantum interference (QI) between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) produces a nonlinear energy-dependent tunnelling probability near the electrode Fermi energy (EF)5,6,7,8. However, tuning such systems is not straightforward, as aligning the frontier orbitals to EF is hard to control9. Here, we instead create a molecular system where constructive QI between the HOMO and LUMO is suppressed and destructive QI between the HOMO and strongly coupled occupied orbitals of opposite phase is enhanced. We use a series of fluorene oligomers containing a central benzothiadiazole10 unit to demonstrate that this strategy can be used to create highly nonlinear single-molecule circuits. Notably, we are able to reproducibly modulate the conductance of a 6-nm molecule by a factor of more than 104.

Tavasli, Mustafa/0000-0002-9466-1111; BATTAL, AHMET/0000-0003-0208-1564; Cameron, Joseph/0000-0001-8622-8353 Two novel heteroleptic iridium(III) acetylacetonate (acac) complexes K3a and K3b were synthesised from cyclometallating ligands of 2-(4'-formylphenyl)quinoline lla and 2-(5'-formylphenyl)quinoline 11b. Complexes K3a and K3b were fully characterised by NMR spectroscopy, mass spectrometry and FT-IR. Differential scanning calorimetry (DSC) and thermal gravimetric analysis (TGA) indicate that both complexes were amorphous solids, stable up to 303 degrees C and 313 degrees C, respectively. Complexes K3a and K3b showed strong, high-energy absorption bands (

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.

Two novel carbazole-based compounds 7a and 7b were synthesised as potential candidates for application in organic electronics. The materials were fully characterised by NMR spectroscopy, mass spectrometry, FT-IR, thermogravimetric analysis, differential scanning calorimetry, cyclic voltammetry, and absorption and emission spectroscopy. Compounds 7a and 7b, both of which were amorphous solids, were stable up to 291oC and 307oC, respectively. Compounds 7a and 7b show three distinctive absorption bands: high and mid energy bands due to locally excited (LE) transitions and low energy bands due to intramolecular charge transfer (ICT) transitions. In dichloromethane solutions compounds 7a and 7b gave emission maxima at 561 nm and 482 nm with quantum efficiencies of 5.4% and 97.4% ± 10%, respectively. At positive potential, compounds 7a and 7b gave two different oxidation peaks, respectively: quasi-reversible at 0.55 V and 0.71 V, and reversible at 0.84 V and 0.99 V. At negative potentials, compounds 7a and 7b only exhibited an irreversible reduction peak at -1.86 V and -1.93 V, respectively.

The development of organic down-converting materials continues to attract attention in hybrid LED technology by obviating the need for non-sustainable rare-earth elements. In this work, a benzodiimidazole-based system (TPA-BDI) has been employed as a down-converting layer in a hybrid organic-inorganic LED device. A commercially available poly(urethane)-based resin is used as the encapsulating material, providing a dilute layer of TPA-BDI that is deposited on top of the GaN-based LED. Crucially, the solution-state emissive performance is generally maintained when encapsulated at low concentrations within this resin. A maximum luminous efficacy of 87 lm W -1 was demonstrated using a 1.0 mg ml -1 concentration of TPA-BDI in the resin. The suitability of using organic down-converters to produce green light from hybrid devices was demonstrated by the excellent repeatability of the device characteristics across a series of encapsulated LEDs.

To rival the performance of modern integrated circuits, single-molecule devices must be designed to exhibit extremely nonlinear current-voltage (I-V) characteristics

The quenching of excitons in organic solar cells can play a significant role in limiting their power conversion efficiency (PCE). In this article, we investigate the effect of a thin layer of hexapropyltruxene inserted at the interface between the electron donor boron subphthalocyanine chloride (SubPc) and its underlying hole contact in planar heterojunction solar cells. We find that a 3.8 nm hexapropyltruxene interlayer between the molybdenum oxide (MoOx) hole contact and SubPc is sufficient to improve PCE in SubPc/C60 fullerene solar cells from 2.6% to 3.0%, a ∼20% performance improvement. While the absorption stays roughly the same, the comparison of external and internal quantum efficiencies reveals a significant increase in SubPc's contribution to the current for light with wavelengths between 520 and 600 nm. Microstructure and surface morphology assessed with in situ Grazing-Incidence Wide-Angle X-Ray Scattering (GIWAXS) and Atomic Force Microscopy (AFM), are evaluated alongside in situ spectroscopic ellipsometry, and photoluminescence measurements. The microstructural investigations demonstrate changes to the surface and bulk of SubPc grown atop a hexapropyltruxene interlayer indicating that the latter acts as a template layer in a similar way as MoOx. However, the improvement in PCE is found to be mainly via reduced exciton quenching at the MoOx contact with the insertion of the hexapropyltruxene layer.

International audience; A facile efficient synthetic tool, Buchwald-Hartwig cross-coupling reaction, for the functionalization of 1,2,4,5tetrazines is presented. Important factors affecting the Buchwald-Hartwig cross-coupling reaction have been optimized. Seven new donor-acceptor tetrazine molecules (TA1-TA7) were conveniently prepared in good to high yields (61%-72%). They have been subsequently engaged in inverse Electron Demand Diels-Alder (iEDDA) reaction with cyclooctyne. The photophysical and electrochemical properties of the new pyridazines have been studied. Some are fluorescent acting as turn-on probes. More importantly two pyridazines (DA3 and DA6) exhibit room temperature phosphorescence (RTP) properties.

Tavasli, Mustafa/0000-0002-9466-1111; BATTAL, Ahmet/0000-0003-0208-1564 Two novel carbazole-based compounds 7a and 7b were synthesised as potential candidates for application in organic electronics. The materials were fully characterised by NMR spectroscopy, mass spectrometry, FTIR, thermogravimetric analysis, differential scanning calorimetry, cyclic voltammetry, and absorption and emission spectroscopy. Compounds 7a and 7b, both of which were amorphous solids, were stable up to 291 degrees C and 307 degrees C, respectively. Compounds 7a and 7b show three distinctive absorption bands: high and mid energy bands due to locally excited (LE) transitions and low energy bands due to intramolecular charge transfer (ICT) transitions. In dichloromethane solutions compounds 7a and 7b gave emission maxima at 561 nm and 482 nm with quantum efficiencies of 5.4% and 97.4% +/- 10%, respectively. At positive potential, compounds 7a and 7b gave two different oxidation peaks, respectively: quasi-reversible at 0.55 V and 0.71 V, and reversible at 0.84 V and 0.99 V. At negative potentials, compounds 7a and 7b only exhibited an irreversible reduction peak at -1.86 V and -1.93 V, respectively. Scientific Research Programme Unit (BAP) of Uludag University [KUAP (F)-2018/14]; Scientific and Technological Research Council of Turkey (TUBITAK)Turkiye Bilimsel ve Teknolojik Arastirma Kurumu (TUBITAK) [2211-C]; Scientific and Technological Research Council of Turkey (TUBITAK)Turkiye Bilimsel ve Teknolojik Arastirma Kurumu (TUBITAK); University of Glasgow; EPSRC ERC Capital Award SchemeUK Research & Innovation (UKRI)Engineering & Physical Sciences Research Council (EPSRC) [EP/S017984/1] This work was supported by the Scientific Research Programme Unit (BAP) of Uludag University [KUAP (F)-2018/14]. Nuray Altinolcek thanks the Scientific and Technological Research Council of Turkey (TUBITAK) for a Ph.D. scholarship for domestic priority areas (2211-C). Dr. Ahmet Battal thanks the Scientific and Technological Research Council of Turkey (TUBITAK) for 2219-International Postdoctoral Research Fellowship Programme for Turkish Citizens. Dr William Peveler acknowledges the University of Glasgow for an LKAS Scholarship, and the EPSRC ERC Capital Award Scheme (EP/S017984/1) for the Duetta instrument.

A novel methodology towards fabrication of multilayer organic devices, employing electrochemical polymer growth to form PEDOT and PEDTT layers, is successfully demonstrated. Moreover, careful control of the electrochemical conditions allows the degree of doping to be effectively altered for one of the polymer layers. Raman spectroscopy confirmed the formation and doped states of the PEDOT/PEDTT bilayer. The electrochemical deposition of a bilayer containing a de-doped PEDTT layer on top of doped PEDOT is analogous to a solution-processed organic semiconductor layer deposited on top of a PEDOT:PSS layer without the acidic PSS polymer. However, the poor solubility of electrochemically deposited PEDTT (or other electropolymerised potential candidates) raises the possibility of depositing a subsequent layer via solution-processing.

Work toward the utilisation of an organic laser as a bacterial growth detector is presented here. The sensor used is an optically excited 2nd order DFB (distributed feedback laser) made of oligofluorene truxene. In the drive towards a practical bacterial growth detector, temperature stability and the optimum growth conditions of bacteria are challenges to be overcome. The resultant DFB laser exhibits a sensitivity of 9 nm/RIU.

Conjugated polymers are an important class of organic semiconductors that can be deposited from solution to make optoelectronic devices. Among them, poly(9,9′-dioctylfluorene) (PFO) has distinctive optical properties arising from its ability to adopt an ordered planar conformation (β phase) from a disordered glassy phase (α phase). The β phase has attractive optical properties, but the precise mechanism of its formation in solution remains unknown. Here, we have combined specifically tailored polymer synthesis and surface-passivation strategies to provide the first spectroscopic characterization of single PFO chains in solution at room temperature. By anchoring PFO molecules at one end on an anti-adherent surface, we show that isolated chains can adopt the β-phase conformation in a solvent-dependent manner. Furthermore, we find that individual PFO chains can reversibly switch multiple times between phases in response to solvent-exchange events. The methodology presented here for polymer synthesis and immobilization is widely applicable to investigate other luminescent polymers. Postprint Postprint

Using a simple -conjugated trimer, EDOT-phenylene-EDOT (where EDOT = 3,4-ethylenedioxythiophene), we evaluate the effect that fluorine substituents have upon changes in conformation, conjugation and oxidation potentials in -conjugated structures. These variations are assessed as a function of the fluorine atom’s propensity to feature in hydrogen and/or halogen bonding with other heteroatoms. The molecular motif was chosen because the EDOT unit presents the possibility of competing O···X or S···X non-covalent contacts (where X = H or F). Such non-bonding interactions are acknowledged to be highly influential in dictating molecular and polymer morphology and inducing changes in certain physical properties. We have studied four compounds, beginning with an unsubstituted bridging phenylene ring and then adding one, two or four fluorine units to the parent molecule. Our studies involve single crystal XRD studies, cyclic voltammetry, absorption spectroscopy and density functional theory calculations to identify the dominant non-covalent interactions and elucidate their effects on the molecules described. Experimental studies have also been carried out on the corresponding electrochemically synthesized polymers to confirm that these non-covalent interactions and their effects persist in polymers. Our findings show that hydrogen bonding and halogen bonding feature in these molecules and their corresponding polymers. ABSTRACT: Using a simple -conjugated trimer, EDOT-phenylene-EDOT (where EDOT = 3,4-ethylenedioxythiophene), we evaluate the effect that fluorine substituents have upon changes in conformation, conjugation and oxidation potentials in -conjugated structures. These variations are assessed as a function of the fluorine atom’s propensity to feature in hydrogen and/or halogen bonding with other heteroatoms. The molecular motif was chosen because the EDOT unit presents the possibility of competing O···X or S···X non-covalent contacts (where X = H or F). Such non-bonding interactions are acknowledged to be highly influential in dictating molecular and polymer morphology and inducing changes in certain physical properties. We have studied four compounds, beginning with an unsubstituted bridging phenylene ring and then adding one, two or four fluorine units to the parent molecule. Our studies involve single crystal XRD studies, cyclic voltammetry, absorption spectroscopy and density functional theory calculations to identify the dominant non-covalent interactions and elucidate their effects on the molecules described. Experimental studies have also been carried out on the corresponding electrochemically synthesized polymers to confirm that these non-covalent interactions and their effects persist in polymers. Our findings show that hydrogen bonding and halogen bonding feature in these molecules and their corresponding polymers.

Low-cost single molecular electrochromic (EC) materials with low toxicity are desirable for EC displays and photonic devices. In this study, new EC materials based on phthalates, an inexpensive class of benzoate materials with relatively simple molecular structure, are designed and prepared. Despite being good candidates for EC devices due to clear colour changes when reduced, devices fabricated using phthalate derivatives (PDs) suffer from a high driving voltage. Herein, we propose a facile strategy of replacing the benzene core with polyaromatic esters to enlarge the conjugated area and to synthesise PDs to lower the driving voltage in EC devices. Additionally, devices show good memory effect (hundreds of seconds), the ability to undergo multiple colour changes and enhanced stability, dependent on the size of the conjugated bridge between the two sides of the molecule. The fabricated EC devices based on polyaromatic esters demonstrate a low driving voltage (−2.6 V). We have shown that the number of aromatic ester rings in the conjugated area is very critical to obtain different colours in this new class of EC materials. This series of EC materials has promising potential for future industry applications due to the vivid colour change upon electrochemical stimulation at a low driving voltage.

P.J.S. and A.L.K. thank the EPSRC for funding under Grants EP/R03480X/1, EP/P02744X/2, and EP/N009908/2. One of the most desirable and advantageous attributes of organic materials chemistry is the ability to tune the molecular structure to achieve targeted physical properties. This can be performed to achieve specific values for the ionization potential or electron affinity of the material, the absorption and emission characteristics, charge transport properties, phase behavior, solubility, processability, and many other properties, which in turn can help push the limits of performance in organic semiconductor devices. A striking example is the ability to make subtle structural changes to a conjugated macromolecule to vary the absorption and emission properties of a generic chemical structure. In this Account, we demonstrate that target properties for specific photonic applications can be achieved from different types of semiconductor structures, namely, monodisperse star-shaped molecules, complex linear macromolecules, and conjugated polymers. The most appropriate material for any single application inevitably demands consideration of a trade-off of various properties; in this Account, we focus on applications such as organic lasers, electrogenerated chemiluminescence, hybrid light emitting diodes, and visible light communications. In terms of synthesis, atom and step economies are also important. The star-shaped structures consist of a core unit with 3 or 4 functional connection points, to which can be attached conjugated oligomers of varying length and composition. This strategy follows a convergent synthetic pathway and allows the isolation of target macromolecules in good yield, high purity, and absolute reproducibility. It is a versatile approach, providing a wide choice of constituent molecular units and therefore varying properties, while the products share many of the desirable attributes of polymers. Constructing linear conjugated macromolecules with multifunctionality can lead to complex synthetic routes and lower atom and step economies, inferior processability, and lower thermal or chemical stability, but these materials can be designed to provide a range of different targeted physical properties. Conventional conjugated polymers, as the third type of structure, often feature so-called “champion” properties. The synthetic challenge is mainly concerned with monomer synthesis, but the final polymerization sequence can be hard to control, leading to variable molecular weights and polydispersities and some degree of inconsistency in the properties of the same material between different synthetic batches. If a champion characteristic persists between samples, then the variation of other properties between batches can be tolerable, depending on the target application. In the case of polymers, we have chosen to study PPV-type polymers with bulky side groups that provide protection of their conjugated backbone from π–π stacking interactions. These polymers exhibit high photoluminescence quantum yields (PLQYs) in films and short radiative lifetimes and are an important benchmark to monodisperse star-shaped systems in terms of different absorption/emission regions. This Account therefore outlines the advantages and special features of monodisperse star-shaped macromolecules for photonic applications but also considers the two alternative classes of materials and highlights the pros and cons of each class of conjugated structure. Publisher PDF

A series of novel star-shaped oligofluorene-thiophene-tetrathiafulvalene systems have been synthesised, following different synthetic routes. Each system incorporates a tetrathiafulvalene redox-active centre and four oligofluorene arms, providing a two-dimensional character of the conjugated backbone. The oligomers differ in the number of fluorene units present in the arms (1 to 4) and the terminal groups at the end of each arm (H or trimethylsilyl). Half-unit oligofluorene systems possessing a 1,3-dithiole-2-one core (a known precursor to the tetrathiafulvalene centre) have been synthesised in order to compare the thermal, optical and electrochemical properties. These half-unit systems consist of a 1,3-dithiole-2-one core fused to a thiophene unit at the 3- and 4- positions. Two oligofluorene arms consisting of 1 to 4 monomer units per arm are positioned at the 4- and 6- positions of the thiophene unit, affording extended conjugation through the thiophene centre. The half-unit systems are found to be moderate emitters in the solution-state, however, the star-shaped systems bearing the tetrathiafulvalene core exhibit inhibited fluorescence in both the solution and solid states. We have demonstrated that the emission of the tetrathiafulvalene systems can be enhanced through the oxidation of the redox-centre followed by a consecutive reaction of the strongly electrophilic tetrathiafulvalene dication with such nucleophiles as water and hydrazine. The result of these reactions leads to an increase in the photoluminescence of these systems, affording the opportunity for the tetrathiafulvalene materials to be used as photonic materials in moisture indicators.

A series of red fluorescent materials (compounds 1-4), which each contain the symmetric fluorene-thiophene-BT-thiophene-fluorene core, is presented along with their performance in solution-processed OLED devices. Extending the molecular conjugation through end-capping with additional fluorene units (compound 2), or through incorporation of donor functionalities (compounds 3 and 4) improves OLED performance relative to the parent compound 1. Notably, incorporating triphenylamine donor groups in compound 3 led to solution-processed OLED devices operating with a peak luminance of 2888 cd m −2 and a low turn-on voltage (3.6 V).

One of the most important non-radiative relaxation processes that limits the quantum yield of a fluorophore is related to aggregation of the molecules in the solid-state causing excimer quenching. To limit this quenching mechanism, the fluorophore can be contained within a well-ordered 3D system that minimises aggregation through rigid bonds and spatial separation in a defined topological construct. Herein, the synthesis, characterisation and application as a down-converter of a new luminescent 3D material (MOF-BTBMBA) that incorporates a building block based on a benzothiadiazole (BT) derivative (BTBMBA) in a metal–organic framework (MOF) is presented. Notably, the photoluminescence quantum yield and hybrid LED performance are significantly improved for the MOF-based device compared to that prepared with the free ligand, highlighting the effectiveness of the rigid scaffold arrangement.

The addition of oleylamine coated Cu2ZnSnS4 (CZTS) nanoparticles to solutions of an organic semiconductor used to fabricate organic field-effect transistors (OFETs) has been investigated. The oligothiophene-based small molecule 5T-TTF and the polymer poly(3-hexylthiophene) (P3HT) were each applied in the transistors with various concentrations of CZTS (5–20%). Atomic force microscopy (AFM) was applied to characterise the surface morphology of the OFETs. The use of 5 and 10 wt% of the CZTS nanoparticles in 5T-TTF and P3HT solutions, respectively, appears to be a simple and effective way of improving OFET performance.

A new triaryl molecule based on a benzene–benzothiadiazole–benzene core has been applied in a WOLED device. This very simple molecule emits from a combination of emissive states (exciton/electromer/exciplex/electroplex) to give white light with CIE coordinates of (0.38, 0.45) and a colour temperature of 4500 K.

Two novel linear oligomers that can be solution-processed to form green organic light-emitting diodes (OLEDs) are reported. Each oligomer has a donor–acceptor structure, incorporating a benzothiadiazole core with bifluorene arms attached at the 4- and 7-positions. Further electron donor behaviour is inferred from a terminal triphenylamine unit in Green 2. The resulting solution-processed OLEDs exhibited excellent performance, with a maximum luminance of 20 388 cd m−2 recorded for Green 2.

Herein, we report synthesis and properties of new multifunctional materials, containing quinoxaline as an acceptor core and differently substituted carbazole moieties as the donors within unsymmetrical D-A-D’ type structures. The compounds exhibit thermally activated delayed fluorescence, luminescence variation in response to external stresses (from green to orange) and emission enhancement in the aggregated state. The effect of substitutions on the different properties is discussed. The investigation suggests that the strength of the donor determines the optical properties of unsymmetrical bipolar emitters. Density functional theory calculations revealed that in the ground and the excited state, electrons of the highest occupied molecular orbitals (HOMOs) are mainly localized on the stronger donor. Mechanochromism studies demonstrated that the bulky tert-butyl groups attached to the carbazole moiety give rise to a hypsochromic effect. It is also associated with the strong reversible colour contrast, in the range of 524–583 nm, in response to external stresses. Using the synthesized compound as an emitter in organic light emitting diode, maximum external quantum efficiency of 10.5% and luminance of 48800 cd.cm−2 were observed.

Thianthrenes have been nearly forgotten as phosphors in recent years, but are now coming back, showing their strong potential in luminescent applications. Here, we present a comprehensive photophysical study of a carbazolyl derivative of thianthrene in different matrices and environments. The diffusion of oxygen is slowed down in the rigid environment of thianthrene organic crystals, suppressing their phosphorescence quenching.Triplet–triplet annihilation is also not significantly active in these systems. Both conditions facilitate the observation of simultaneous fluorescence and phosphorescence emissions at room temperature, in air, giving origin to strong white luminescence. Moreover, the color coordinates of the dual fluorescence–phosphorescence white emission, which is observed only in rigid amorphous media and in crystals, can be tuned.

The influence of phenyl linkage and donor strength on the photophysical properties of new derivatives of quinoxaline-containing iminodibenzyl and iminostilbene moieties is studied. The donor-acceptor derivatives showed dual thermally activated delayed fluorescence (TADF) and room temperature phosphorescence (RTP) despite a large energy gap between the excited singlet and triplet states (ca. 0.5 eV). This extremely rare observation is explained by the twisted and rigidified structure of the iminodibenzyl moiety.

The article presents a novel impedance spectroscopy based technique designed to characterise organic light emitting diodes (OLED) during operation. A number of devices based on NPB (N,N′-di(1-naphthyl)-N,N′-diphenyl-(1,1′-biphenyl)-4,4′-diamine) and TPBi (2,2′,2′′-(1,3,5-benzinetriyl)-tris(1-phenyl-1-H-benzimidazole)) conducting layers, CBP (4,4′-bis(N-carbazolyl)-1,1′-biphenyl) as a host and BPTZ-DBTO2 (3,6-bis(10H-phenothiazine-10-yl)-9H-fluorene-[dibenzothiophene-S,S-dioxide]) as an emitter were taken as an example to validate the method. Using equivalent electrical circuits, values of capacitance and conductivity of both hole- (HTL) and electron-transport (ETL) layers were determined and analysed separately. Those parameters, as well as current–voltage characteristics, were used to calculate (i) mobility (μ, cm2 V−1 s−1) of both types of charge carriers, (ii) charge density (n, cm−3) of the charge carriers, and (iii) electric field intensity (E, V m−1) in both transport layers as functions of the applied voltage.

The influence of different thiophene donor units on electrochemical and spectroscopic properties of benzothiadiazole based donor–acceptor π-conjugated organic materials is studied. Two different structure modification vectors of the donor units are being considered – one addressing the intermolecular interactions through off-conjugation side chain architecture, and the other focusing on intramolecular interactions tuned by in-conjugation substituents. Electrochemical and simultaneous in situ EPR-UV-Vis-NIR spectroelectrochemical studies of the oxidative (p-) and reductive (n-) doping processes, which are responsible for the optoelectronic properties of these materials, revealed their disparate course and dissimilar effects of redox reactions of the conjugated π-bond. While p-doping prevalent species were found to comprise intensively interacting spin bearing and spinless charge carriers, the n-doping state was found to involve only one type of negatively charged carrier, with spin carrying species being selectively generated at due cathodic potentials. No spin pairing of these negative polarons was observed with their increasing population behaving like a collection of localised charge carriers. Qualitative and quantitative comparisons between the p- and n-doping carrier populations provided independent support for the spin pairing phenomena of positive charge carriers. Steric effects of varying alkyl side chain substitution have demonstrated predominant impact on the electrochemical properties of investigated polymers, and, thereto related, stability of n-doped state, while mesomeric effects of different 3,4-ethylenechalcogenide thiophene functionalities have been found to shape the energy level related spectral properties of these polymers, with particular reference to p-doping induced charged states. These findings provide new insights into the factors requiring attention during structure tailoring of donor–acceptor assemblies for organic optoelectronic applications.

The search for a clean, renewable source of energy as a replacement for fossil fuels has been at the forefront of scientific, economic and political research for the past few decades. Of the commonly investigated techniques, one strong contender that fits this role extremely well is solar power. The ability to harvest energy from sunlight incident on the Earth’s surface in an efficient and cost-effective manner would alleviate the global energy crisis with relative ease – more energy reaches the Earth from the Sun in one hour than all the energy consumed on the planet in an entire year. Progress has been both fast and expansive, with a large number of research groups across the globe finely tuning and improving solar-harvesting technology. Organic solar cells show huge promise for future energy-harvesting because they allow very low-cost production through the use of low-temperature fabrication techniques, such as roll-to-roll processing or inkjet printing. Organic solar cell materials can also be made to be flexible and semi-transparent and are extremely lightweight compared with the current market-leading silicon-based alternatives. This chapter aims to give a concise overview of some of the progress made to date, with attention focused on prepared and tested state-of-the-art, high-performance materials.