Oxygen-Tolerant Near-Infrared Organic Long-Persistent Luminescent Copolymers.

Organic materials exhibiting long-lasting emission in the near infrared are expected to have applications in bio-imaging and other areas. Although room temperature phosphorescence and thermally activated delayed fluorescence display long-lived emission of approximately one minute, organic long-persistent luminescence (OLPL) systems with a similar emission mechanism to inorganic persistent emitters can emit for several hours at room temperature. In particular OLPL with a hole-diffusion mechanism can function even in the presence of oxygen. However, ionic materials lack long-term stability in neutral organic host owing to aggregation and phase separation. In this study, we synthesized polymers with stable near-infrared persistent luminescence at room temperature via the copolymerization of electron donors and acceptors. The copolymers exhibit long-persistent luminescence (LPL) at temperatures below the glass transition temperature and can be excited by approximately the entire range of visible light. LPL properties and spectra can be controlled by the dopant.

A Rigid Multiple Resonance Thermally Activated Delayed Fluorescence Core Toward Stable Electroluminescence and Lasing.

The investigation of organic light-emitting diodes (OLEDs) and organic laser devices with thermally activated delayed fluorescence (TADF) molecules is emerging due to the potential of harnessing triplets. In this work, a boron/nitrogen multiple-resonance TADF polycyclic framework fusing carbazole units (CzBNPh) was proposed. CzBNPh exhibited a narrowband emission (<30 nm), a unity photoluminescence quantum yield, and a fast radiative rate. Consequently, CzBNPh demonstrated a low distributed feedback (DFB) lasing threshold of 0.68 µJ cm-2 . Furthermore, the stimulated emission zone of CzBNPh was effectively separated from its singlet and triplet absorption, thereby minimizing the singlet-triplet annihilation under long-pulsed excitation ranging from 20 µs to 2.5 ms. Significantly, the enhanced rigid molecular conformation, thermal stability, and photo-stability resulted in improved lasing and electroluminescence stability compared to that of 5,9-diphenyl-5,9-diaza-13b-boranaphtho[3,2,1-de]anthracene (DABNA)-core. These findings indicate the potential of CzBN-core as a promising framework for achieving long-pulsed wave and electrically-pumped lasing in the future.

Organic long-persistent luminescence stimulated by visible light in p-type systems based on organic photoredox catalyst dopants.

Organic long-persistent-luminescent (OLPL) materials demonstrating hour-long photoluminescence have practical advantages in applications owing to their flexible design and easy processability. However, the energy absorbed in these materials is typically stored in an intermediate charge-separated state that is unstable when exposed to oxygen, thus preventing persistent luminescence in air unless oxygen penetration is suppressed through crystallization. Moreover, OLPL materials usually require ultraviolet excitation. Here we overcome such limitations and demonstrate amorphous OLPL systems that can be excited by radiation up to 600 nm and exhibit persistent luminescence in air. By adding cationic photoredox catalysts as electron-accepting dopants in a neutral electron-donor host, stable charge-separated states are generated by hole diffusion in these blends. Furthermore, the addition of hole-trapping molecules extends the photoluminescence lifetime. By using a p-type host less reactive to oxygen and tuning the donor-acceptor energy gap, our amorphous blends exhibit persistent luminescence stimulated by visible light even in air, expanding the applicability of OLPL materials.

Organic long persistent luminescence.

Long persistent luminescence (LPL) materials-widely commercialized as 'glow-in-the-dark' paints-store excitation energy in excited states that slowly release this energy as light. At present, most LPL materials are based on an inorganic system of strontium aluminium oxide (SrAl2O4) doped with europium and dysprosium, and exhibit emission for more than ten hours. However, this system requires rare elements and temperatures higher than 1,000 degrees Celsius during fabrication, and light scattering by SrAl2O4 powders limits the transparency of LPL paints. Here we show that an organic LPL (OLPL) system of two simple organic molecules that is free from rare elements and easy to fabricate can generate emission that lasts for more than one hour at room temperature. Previous organic systems, which were based on two-photon ionization, required high excitation intensities and low temperatures. By contrast, our OLPL system-which is based on emission from excited complexes (exciplexes) upon the recombination of long-lived charge-separated states-can be excited by a standard white LED light source and generate long emission even at temperatures above 100 degrees Celsius. This OLPL system is transparent, soluble, and potentially flexible and colour-tunable, opening new applications for LPL in large-area and flexible paints, biomarkers, fabrics, and windows. Moreover, the study of long-lived charge separation in this system should advance understanding of a wide variety of organic semiconductor devices.

Synthesis of a π-Extended Double [9]Helicene.

Double helicenes are appealing chiral frameworks. Their π-extension is desirable to achieve (chir)optical response in the visible and near-infrared (NIR) region, but access to higher double [n]helicenes (n≥8) has remained challenging. Herein, we report an unprecedented π-extended double [9]helicene (D9H), unambiguously revealing its structure by single-crystal X-ray diffraction. D9H shows remarkable NIR emission from 750 to 1100 nm with a high photoluminescence quantum yield of 18 %. In addition, optically pure D9H exhibits panchromatic circular dichroism with a notable dissymmetry factor (gCD ) of 0.019 at 590 nm, which is among the highest in the visible region for reported helicenes.

Graphene-Pyrene Nanocomposites Obtained Using Azide Chemistry.

In this study we describe a simple and fast procedure for the covalent functionalization of pristine graphene with a pyrene-terminated alkylazide, transformed in a highly reactive radical by thermal activation. The functionalized graphene sheets showed enhanced dispersibility in organic solvents compared to the pristine ones, thus enhancing their solution processability and compatibility with solvents or polymers. The relative improvement of solubility estimated form the absorption spectra was ≈60% in CHCl3 and ≈1200% in THF. The obtained materials were characterized by optical absorption spectroscopy, photoemission spectroscopy, infrared spectroscopy and X-rays photoelectron spectroscopy. The presence of the pyrene photoemitting chromophore in the grafting unit allowed to monitor the successful grafting and to confirm the effectiveness of the alkylazide to improve graphene solubility even when present in small amounts on the graphene surface.

Graphene-Like Conjugated Molecule as Hole-Selective Contact for Operationally Stable Inverted Perovskite Solar Cells and Modules.

Further enhancing the operational lifetime of inverted-structure perovskite solar cells (PSCs) is crucial for their commercialization, and the design of hole-selective contacts at the illumination side plays a key role in operational stability. In this work, the self-anchoring benzo[rst]pentaphene (SA-BPP) is developed as a new type of hole-selective contact toward long-term operationally stable inverted PSCs. The SA-BPP molecule with a graphene-like conjugated structure shows a higher photostability and mobility than that of the frequently-used triphenylamine and carbazole-based hole-selective molecules. Besides, the anchoring groups of SA-BPP promote the formation of a large-scale uniform hole contact on ITO substrate and efficiently passivate the perovskite absorbers. Benefiting from these merits, the champion efficiencies of 22.03% for the small-sized cells and 17.08% for 5 × 5 cm2 solar modules on an aperture area of 22.4 cm2 are achieved based on this SA-BPP contact. Also, the SA-BPP-based device exhibits promising operational stability, with an efficiency retention of 87.4% after 2000 h continuous operation at the maximum power point under simulated 1-sun illumination, which indicates an estimated T80 lifetime of 3175 h. This novel design concept of hole-selective contacts provides a promising strategy for further improving the PSC stability.

Synthesis of zigzag- and fjord-edged nanographene with dual amplified spontaneous emission.

We report the synthesis of a dibenzodinaphthocoronene (DBDNC) derivative as a novel nanographene with armchair, zigzag, and fjord edges, which was characterized by NMR and X-ray crystallography as well as infrared (IR) and Raman spectroscopies. Ultrafast transient absorption (TA) spectroscopy revealed the presence of stimulated emission signals at 655 nm and 710 nm with a relatively long lifetime, which resulted in dual amplified spontaneous emission (ASE) bands under ns-pulsed excitation, indicating the promise of DBNDC as a near-infrared (NIR) fluorophore for photonics. Our results provide new insight into the design of nanographene with intriguing optical properties by incorporating fjord edges.

Excited states engineering enables efficient near-infrared lasing in nanographenes.

The spectral overlap between stimulated emission (SE) and absorption from dark states (i.e. charges and triplets) especially in the near-infrared (NIR), represents one of the most effective gain loss channels in organic semiconductors. Recently, bottom-up synthesis of atomically precise graphene nanostructures, or nanographenes (NGs), has opened a new route for the development of environmentally and chemically stable materials with optical gain properties. However, also in this case, the interplay between gain and absorption losses has hindered the attainment of efficient lasing action in the NIR. Here, we demonstrate that the introduction of two fluoranthene imide groups to the NG core leads to a more red-shifted emission than the precursor NG molecule (685 vs. 615 nm) and also with a larger Stokes shift (45 nm vs. 2 nm, 1026 cm-1vs. 53 cm-1, respectively). Photophysical results indicate that, besides the minimisation of ground state absorption losses, such substitution permits to suppress the detrimental excited state absorption in the NIR, which likely arises from a dark state with charge-transfer character and triplets. This has enabled NIR lasing (720 nm) from all-solution processed distributed feedback devices with one order of magnitude lower thresholds than those of previously reported NIR-emitting NGs. This study represents an advance in the field of NGs and, in general, organic semiconductor photonics, towards the development of cheap and stable NIR lasers.

Model study of CO inhibition of [NiFe]hydrogenase.

We propose a modified mechanism for the inhibition of [NiFe]hydrogenase ([NiFe]H(2)ase) by CO. We present a model study, using a NiRu H(2)ase mimic, that demonstrates that (i) CO completely inhibits the catalytic cycle of the model compound, (ii) CO prefers to coordinate to the Ru(II) center rather than taking an axial position on the Ni(II) center, and (iii) CO is unable to displace a hydrido ligand from the NiRu center. We combine these studies with a reevaluation of previous studies to propose that, under normal circumstances, CO inhibits [NiFe]H(2)ase by complexing to the Fe(II) center.

Long-Persistent Luminescence from an Exciplex-Based Organic Light-Emitting Diode.

Organic long-persistent luminescent systems (OLPLs) exhibiting long-lasting emission after photoexcitation consist of organic electron donors and acceptors, that are widely used in organic light-emitting diodes (OLEDs). Although OLPLs and OLEDs include very similar excitonic processes, long-lasting emission has never been observed in OLEDs. This study confirms the presence of long-persistent luminescence (LPL) under electrical excitation.

Thermally activated processes in an organic long-persistent luminescence system.

Glow-in-the-dark materials can store absorbed photon energy and emit light for long periods of time. While inorganic long-persistent luminescence (LPL) materials are crystalline and often require rare metals, organic LPL (OLPL) materials are flexible and require no rare metals. The emission process of OLPL systems consists of photoinduced charge separation, charge accumulation, and emission from charge recombination. Although emission processes of OLPL systems have been investigated, the charge separation and accumulation processes remain enigmatic. In this study, we investigated the charge carrier dynamics of a binary OLPL system comprising of electron donors and acceptors. We confirmed the presence of thermal activation processes, thermally activated delayed fluorescence and thermoluminescence in the OLPL system.

Influence of energy gap between charge-transfer and locally excited states on organic long persistence luminescence.

Organic long-persistent luminescence (LPL) is an organic luminescence system that slowly releases stored exciton energy as light. Organic LPL materials have several advantages over inorganic LPL materials in terms of functionality, flexibility, transparency, and solution-processability. However, the molecular selection strategies for the organic LPL system still remain unclear. Here we report that the energy gap between the lowest localized triplet excited state and the lowest singlet charge-transfer excited state in the exciplex system significantly controls the LPL performance. Changes in the LPL duration and spectra properties are systematically investigated for three donor materials having a different energy gap. When the energy level of the lowest localized triplet excited state is much lower than that of the charge-transfer excited state, the system exhibits a short LPL duration and clear two distinct emission features originating from exciplex fluorescence and donor phosphorescence.

Organic Long-Persistent Luminescence from a Thermally Activated Delayed Fluorescence Compound.

Organic long-persistent luminescence (OLPL) is one of the most promising methods for long-lived-emission applications. However, present room-temperature OLPL emitters are mainly based on a bimolecular exciplex system which usually needs an expensive small molecule such as 2,8-bis(diphenyl-phosphoryl)dibenzo[b,d]thiophene (PPT) as the acceptor. In this study, a new thermally activated delayed fluorescence (TADF) compound, 3-(4-(9H-carbazol-9-yl)phenyl)acenaphtho[1,2-b]pyrazine-8,9-dicarbonitrile (CzPhAP), is designed, which also shows OLPL in many well-known hosts such as PPT, 2,2',2″-(1,3,5-benzinetriyl)-tris(1-phenyl-1-H-benzimidazole) (TPBi), and poly(methyl methacrylate) (PMMA), without any exciplex formation, and its OLPL duration reaches more than 1 h at room temperature. Combining the low cost of PMMA manufacture and flexible designs of TADF molecules, pure organic, large-scale, color tunable, and low-cost room-temperature OLPL applications become possible. Moreover, it is found that the onset of the 77 K afterglow spectra from a TADF-emitter-doped film is not necessarily reliable for determining the lowest triplet state energy level. This is because in some TADF-emitter-doped films, optical excitation can generate charges (electron and holes) that can later recombine to form singlet excitons during the phosphorescence spectrum measurement. The spectrum taken in the phosphorescence time window at low temperature may consequently consist of both singlet and triplet emission.

Wide-Range Tuning and Enhancement of Organic Long-Persistent Luminescence Using Emitter Dopants.

Most long-persistent luminescent (LPL) materials, which slowly release energy absorbed from ambient light, are based on inorganic compounds. Organic long-persistent luminescent (OLPL) systems have advantages over inorganic LPL materials in terms of solubility, transparency, and flexibility. Here, the characteristics of OLPL emission are improved by doping emitter molecules into an OLPL matrix. Greenish-blue to red and even warm white emission are achieved by energy transfer from exciplex in the OLPL matrix to the emitter dopants. The dopants also improve brightness and emission duration through efficient radiative decay and the trapping of electrons, respectively. This technique will enable the development of a wide range of organic glow-in-the-dark paints.

Organic Long-Persistent Luminescence from a Flexible and Transparent Doped Polymer.

Long-persistent luminescence (LPL) materials have a wide range of applications, such as in architectural decorations, safety signs, watch dials, and glow-in-the-dark toys. Present LPL materials based on inorganics must be processed into powders and blended with polymer matrices before use. However, micropowders of inorganic LPL materials show poor compatibility with common polymers, limiting the mechanical properties and transparency of the composites. Here, a polymer-based organic LPL (OLPL) system that is flexible, transparent, and solution processable is reported. Following low-power excitation at room temperature, this polymer-based OLPL system exhibits LPL after phosphorescence from the donor.

A near-infrared organic light-emitting diode based on an Yb(iii) complex synthesized by vacuum co-deposition.

Yb(DBM)3(DPEPO), an emitter, was directly synthesized on a substrate by the vacuum co-deposition of the precursor Yb(DBM)3(H2O)2 and the ligand DPEPO. OLEDs incorporating the co-deposited emitting layer (Yb(DBM)3(H2O)2 : DPEPO molar ratio = 1 : 1) achieved an ηEQE value of 0.15% at 1.0 mA cm-2.

Afterglow Organic Light-Emitting Diode.

An afterglow organic light-emitting diode (OLED) that displays electroluminescence with long transient decay after it is turned off is demonstrated. This OLED exhibits blue and green dual emission originating from fluorescence and phosphorescence, respectively. A phosphorescence lifetime of 4.3 s is achieved.

Exfoliation of graphite into graphene in polar solvents mediated by amphiphilic hexa-peri-hexabenzocoronene.

A water-soluble surfactant consisting of hexa-peri-hexabenzocoronene (HBC) as hydrophobic aromatic core and hydrophilic carboxy substituents was synthesized. It exhibited a self-assembled nanofiber structure in the solid state. Profiting from the π interactions between the large aromatic core of HBC and graphene, the surfactant mediated the exfoliation of graphite into graphene in polar solvents, which was further stabilized by the bulky hydrophilic carboxylic groups. A graphene dispersion with a concentration as high as 1.1 mg L(-1) containing 2-6 multilayer nanosheets was obtained. The lateral size of the graphene sheets was in the range of 100-500 nm based on atomic force microscope (AFM) and transmission electron microscope (TEM) measurements.

A [NiFe]hydrogenase model that catalyses the release of hydrogen from formic acid.

We report the decomposition of formic acid to hydrogen and carbon dioxide, catalysed by a NiRu complex originally developed as a [NiFe]hydrogenase model. This is the first example of H2 evolution, catalysed by a [NiFe]hydrogenase model, which does not require additional energy.