Thermally activated delayed fluorescence and high-contrast mechanochromism of anthrone-based donor-acceptor systems

Funding: This project was funded by the European Union’s Horizon 2020 Research and Innovation Programme under the Marie Skłodowska-Curie grant agreement no. 891606 (TADFNIR). The authors thank the Engineering and Physical Sciences Research Council for funding (EP/P010482/1).The development of materials that emit in the deep red to near-infrared region of the spectrum has attracted significant attention on account of their potential as optical sensing and imaging reagents in biology. We report herein the synthesis and optoelectronic characterization of four anthraquinone-based emitters T-tBuCz-AQ, T-MeOCz-AQ, C-tBuCz-AQ, and C-MeOCz-AQ, and two pyrazoloanthrone-based emitters tBuCz-PA and DMAC-PA. Depending on the donor, these compounds emit between 640-750 nm in the neat film, while the emission of the 10 wt% doped films in PMMA are blue-shifted to between 600-700 nm and have low photoluminescence quantum yields of between 2.6-6.6%. Of these compounds, T-tBuCz-AQ, T-MeOCz-AQ, and C-tBuCz-AQ exhibited thermally activated delayed fluorescence in 10 wt% doped films in PMMA, while the crystals of T-tBuCz-AQ also showed TADF. Compound tBuCz-PA showed highcontrast and reversible PL response upon mechanical grinding and hexane fuming.Publisher PDFPeer reviewe

Highly fluorescent emitters based on triphenylamine‐π‐triazine (D‐π‐A) system : effect of extended conjugation on singlet‐triplet energy gap

SK acknowledges the financial support from European Union's Horizon 2020 research and innovation programme under Marie Skłodowska Curie Individual Fellowship (MCIF; Agreement No. 748430‐THF‐OLED).Three D‐π‐A type linearly‐extended emitters, based on diphenylamine ( DPA ) as the donor and 2,4,6‐triphenyl‐1,3,5‐triazine ( TRZ ) as the acceptor, were synthesized and their optoelectronic properties characterized. The introduction of an additional phenyl or phenylethynyl π‐spacer results in an enhancement of the molar extinction coefficient and a systematic bathochromic shift of the charge‐transfer transition in the absorption spectra. A mirrored bathochromic shift in the photoluminescence spectra is also observed with increasing conjugation of the bridge moiety. All three compounds show high photoluminescence quantum yields and moderate singlet‐triplet excited state energy gaps, ΔE ST, of 0.26‐0.37 eV were observed in 10 wt% doped films in mCP as the host matrix.Publisher PDFPeer reviewe

A tale of two tables

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Rational molecular design of efficient yellow-red dendrimer TADF for solution-processed OLEDs : a combined effect of substitution position and strength of the donors

Funding: Changfeng Si thanks the China Scholarship Council (201806890001). Dianming Sun acknowledges support from the Royal Academy of Engineering Enterprise Fellowship (EF2122-13106). We thank EPSRC (EP/W015137/1, EP/W524505/1) for financial support. Open Access funding enabled and organized by Projekt DEAL.The development of high-performance solution-processed red organic light-emitting diodes (OLEDs) remains a challenge, particularly in terms of maintaining efficiency at high luminance. Here, we designed and synthesized four novel orange-red thermally activated delayed fluorescence (TADF) dendrimers that are solution-processable: 2GCzBP , 2DPACzBP , 2FBP2GCz and 2FBP2DPACz . We systematically investigated the effect of substitution position and strength of donors on the optoelectronic properties. The reverse intersystem crossing rate constant (kRISC) of the emitters having donors substituted at positions 11 and 12 of the dibenzo[a,c]phenazine (BP) is more than 10-times faster than that of compounds substituted having donors substituted at positions 3 and 6. Compound 2DPACzBP , containing stronger donors than 2GCzBP , exhibits a red-shifted emission and smaller singlet-triplet energy splitting, ΔEST, of 0.01 eV. The solution-processed OLED with 10 wt% 2DPACzBP doped in mCP emitted at 640 nm and showed a maximum external quantum efficiency (EQEmax) of 7.8%, which was effectively maintained out to a luminance of 1,000 cd m−2. Such a device∙s performance at relevant display luminance is among the highest for solution-processed red TADF OLEDs. The efficiency of the devices was improved significantly by using 4CzIPN as an assistant dopant in a hyperfluorescence (HF) configuration, where the 2DPACzBP HF device shows an EQEmax of 20.0% at λEL of 605 nm and remains high at 11.8% at a luminance of 1,000 cd m−2, which makes this device one of the highest efficiency orange-to-red HF SP-OLEDs to date.Peer reviewe

Physical and photophysical properties of a linear copper(I) complex of a bulky acenapthene-based NHC ligand

CFRM and EZ-C wish to thank the Engineering and Physical Sciences Research Council (EP/M02105X/1 and EP/R035164/1) for financial support. We would like to thank the Engineering and Physical Sciences Research Council and CRITICAT Centre for Doctoral Training for financial support (Ph.D. studentship to B. H.; EP/L016419/1).We report the first example of a charge-neutral linear 2-coordinate copper(I) complex bearing a sterically demanding acenaphthoimidazolylidene-based N-heterocyclic carbene ligand. The identity and geometry of the complex was confirmed by single-crystal XRD (X-Ray Diffraction) analysis. The complex is poorly emissive at room temperature, showing either ligand-centered (LC) emission at around 340 nm when excited at 300 nm or ligand-to-ligand charge-transfer (LLCT) emission at around 540 nm when excited at 420 nm; in chloroform, dual emission is observed upon photoexcitation at 300 nm. Nanosecond emission lifetimes were recorded for these processes. This is the first example of emissive linear copper(I) complexes containing this bulky NHC ligand.PostprintPeer reviewe

Near-infrared fluorescence of silicon phthalocyanine carboxylate esters

EZ-C acknowledges the University of St Andrews for financial support. We are grateful to the EPSRC for financial support from grant EP/M02105X/1 and the European Research Council for financial support from grant 321305. I.D.W.S. acknowledges a Royal Society Wolfson Research Merit Award.Seven silicon(IV) phthalocyanine carboxylate esters (SiPcs, 1–7 ) with non-, partially- and per-fluorinated aliphatic (linear or branched at the alpha-carbon) and aromatic ester groups have been synthesized, their solid-state structures determined and their optoelectronic properties characterized. The SiPcs exhibit quasi-reversible oxidation waves (vs. Fc+/Fc) at 0.58–0.75 V and reduction waves at −0.97 to −1.16 V centered on the phthalocyanine ring with a narrow redox gap range of 1.70–1.75 V. Strong absorbance in the near-infrared (NIR) region is observed for 1–7 with the lowest-energy absorption maximum (Q band) varying little as a function of ester between 682 and 691 nm. SiPcs 1–7 fluorescence in the near-infrared with emission maxima at 691–700 nm. The photoluminescence quantum yields range from 40 to 52%. As a function of esterification, the SiPcs 1–7 exhibit moderate-to-good solubility in chlorinated solvents, such as 1,2-dichlorobenzene and chloroform.Publisher PDFPeer reviewe

Solubilised bright blue-emitting iridium complexes for solution processed OLEDs

EZ-C acknowledges the University of St Andrews for financial support. IDWS and AKB acknowledge support from EPSRC (EP/J01771X). The authors would like to thank the Engineering and Physical Sciences Research Council for financial support for Adam Henwood: EPSRC DTG Grants: EP/J500549/1; EP/K503162/1; EP/L505097/1.Combining a sterically bulky, electron-deficient 2-(2,4-difluorophenyl)-4-(2,4,6- trimethylphenyl)pyridine (dFMesppy) cyclometalating C^N ligand with an electron rich, highly rigidified 1,1’-(α,α’-o-xylylene)-2,2’-biimidazole (o-xylbiim) N^N ligand gives an iridium complex, [Ir(dFMesppy)2(o-Xylbiim)](PF6), that achieves extraordinarily bright blue emission (ΦPL = 90%; λmax = 459 nm in MeCN) for a cationic iridium complex. This complex is compared with two reference complexes bearing 4,4’-di-tert-butyl-2,2’- bipyridine, and solution-processed organic light emitting diodes (OLEDs) have been fabricated from these materials.Publisher PDFPeer reviewe

Highly twisted α-diketone-based thermally activated delayed fluorescence emitters and their use in organic light-emitting diodes

AKG is grateful to the Royal Society for Newton International Fellowship NF171163. We acknowledge support from the Engineering and Physical Sciences Research Council of the UK (grants EP/P010482/1 and EP/L017008/1). We are also grateful for financial support from the University of St Andrews Restarting Research and Restarting Interdisciplinary Research Funding Schemes (SARRF and SARIRF) which are funded through the Scottish Funding Council grant reference SFC/AN/08/020.We have designed a highly twisted small TADF emitter PXZ-α-DK based on an a-diketone (α-DK) as a strong acceptor and phenoxazine (PXZ) as a strong donor to obtain red-shifted emission in comparison to the equivalent a-diketone linked to 9,9-dimethyl-9,10-dihydroacridine (DMAC). The PXZ-α-DK shows emission at 586 nm and DMAC-α-DK shows emission at 548 nm in 1,3-bis(N-carbazolyl)benzene (mCP) host at 1.5 wt% doping of the emitter, with short-delayed lifetimes of 6.9 μs for PXZ-α-DK and 7.6 μs for DMAC-α-DK. OLEDs fabricated using these emitters show green electroluminescence at 555 nm for DMAC-α-DK, with a maximum external quantum efficiency, EQEmax, of 6.3%, and orange electroluminescence at 585 nm for PXZ-α-DK, with an EQEmax of 0.8%. We corroborate the optoelectronic properties of these emitters with DFT calculations.PostprintPeer reviewe

Stable 6H organic-inorganic hybrid lead perovskite and competitive formation of 6H and 3C perovskite structure with mixed A cations

We thank the Chinese Scholarship Council for Ph.D. Studentship support (to JT). Computational resources have been provided by the Consortium des Équipements de Calcul Intensif (CÉCI), funded by the Fonds de la Recherche Scientifique de Belgique (F.R.S.-FNRS) under grant no. 2.5020.11. D.B. is an FNRS Research Director.We report the synthesis and properties of a new organic–inorganic hybrid lead perovskite (OIHP), azetidinium lead bromide (AzPbBr3), possessing the 6H perovskite structure (space group P63/mmc with a = 8.745 Å and c = 21.329 Å). This compound has a band gap of 2.81 eV and remains stable for >6 months in the ambient environment. DFT simulations are in fairly good agreement with experiments and indicate that AzPbBr3 is a direct band gap semiconductor. A partial solid solution with the cubic (3C) perovskite methylammonium lead bromide (Az1–xMAxPbBr3) is possible. In Az-rich 6H compositions the lattice volume and band gap are invariant with x (≤0.3), whereas in the MA-rich 3C phase (0.8 ≤ x ≤ 1.0) the lattice parameters and band gap increase with increasing Az content. Although the relatively large band gap of AzPbBr3 makes it unsuitable for photovoltaic applications, the results indicate Az+ is a suitable alternative organic A cation for band gap tuning of OHIPs.PostprintPeer reviewe

A luminescent 1D silver polymer containing [2.2]paracyclophane ligands

Funding: UK EPSRC Grant Number(s) EP/P014082/1, EP/M02105X/1, EP/R035164/1).[2.2]Paracyclophane scaffolds have seen limited use as building blocks in supramolecular chemistry. Here, we report the synthesis and characterization of a 1D coordination polymer consisting of silver(I) ions bound to a [2.2]paracyclophane scaffold functionalized with two 4-pyridyl units. The structure of the polymer has been determined from single crystal X-ray diffraction analysis and reveals two different silver coordination motifs that alternate along the 1D coordination polymer. The coordination polymer exhibits strong blue and sky-blue fluorescence in solution and in the crystalline solid state, respectively.Publisher PDFPeer reviewe