A review of fused-ring carbazole derivatives as emitter and/or host materials in organic light emitting diode (OLED) applications

This review focuses on fused-ring carbazole derivatives, their molecular design, electronic and photophysical properties, and in particular their applications as the emitter and/or the host material in the emitting layer of organic light emitting diodes (OLEDs), with emphasis on recent developments. This review is timely because of the rapidly expanding research into fused-ring carbazoles, predominantly indolocarbazole, indenocarbazole, benzofurocarbazole, benzothienocarbazole and diindolocarbazole derivatives. To our knowledge this class of materials has not been reviewed previously. The appeal of fused-ring carbazoles is their extended π-electron systems with good thermal stability, tunable frontier orbital energies that enable a wide gamut (red, green, blue and white) emission colour, high photoluminescence quantum yields, and versatility for chemical functionalisation at different sites, leading to outstanding OLED efficiencies. This review is divided into sections according to the molecules’ role in OLEDs: namely, as conventional luminescent emitters – especially in the deep-blue region; as state-of-the-art hosts for phosphorescent iridium-based emitters; as thermally activated delayed fluorescence (TADF) emitters with high external quantum efficiency; and as multiresonance (MR) emitters with unprecedented high colour purity. We conclude by highlighting the challenges and the great opportunities for fused-ring carbazole derivatives in OLEDs and other optoelectronic applications

Arylsilanes and siloxanes as optoelectronic materials for organic light-emitting diodes (OLEDs)

Organic light emitting diodes (OLEDs) are currently receiving much attention for applications in new generation full-colour flat-panel and flexible displays and as sources for low energy solid-state lighting. Arylsilanes and siloxanes have been extensively studied as components of OLEDs, mainly focusing on optimizing the physical and electronic properties of the light-emitting layer and other functional layers within the OLED architecture. Arylsilanes and siloxanes display the advantages of good solubility in common organic solvents and excellent resistance to thermal, chemical and irradiation degradations. In this review, we summarize the recent advances in the utilization of arylsilanes and siloxanes as fluorophore emitters, hosts for phosphor emitters, hole and exciton blocking materials, and as electron and hole transporting materials. Finally, perspectives and challenges related to arylsilanes and siloxanes for OLED applications are proposed based on the reported progress and our own opinions

Dinuclear metal complexes: multifunctional properties and applications

The development of metal complexes for optoelectronic applications is a fertile area of research. In contrast to the rigorous development of mononuclear metal complexes, dinuclear species have been less well studied and their fundamental chemistry and applications are under-explored. However, dinuclear species present special properties and functions compared with mononuclear species as a consequence of tuning the bridging ligands, the cyclometalated ligands or the two metal centers. More recently, dinuclear species have enabled important breakthroughs in the fields of OLEDs, photocatalytic water splitting and CO2 reduction, DSPEC, chemosensors, biosensors, PDT, smart materials and so on. Here we present an overview of recent developments of dinuclear metal complexes, their multifunctional properties and their various applications. The relationship between structure and property of dinuclear species and important factors which influence device performance are discussed. Finally, we illustrate some challenges and opportunities for future research into dinuclear metal complexes. This review aims to provide an up-to-date summary and outlook of functional dinuclear metal complexes and to stimulate more researchers to contribute to this exciting interdisciplinary field

Synthesis of Tetracyclic 2,3-Dihydro-1,3-diazepines from a Dinitrodibenzothiophene Derivative

Triply fused 1,3-diazepine derivatives have been obtained by acidic reduction of rotationally locked and sterically hindered nitro groups in the presence of an aldehyde or ketone. The nitro groups are sited on adjacent rings of a dicyanodibenzothiophene-5,5-dioxide, which also displays fully reversible two-electron-accepting behavior. The synthesis, crystallographically determined molecular structures, and aspects of the electronic properties of these new molecules are presented

Experimental Evidence for Quantum Interference and Vibrationally Induced Decoherence in Single-Molecule Junctions

We analyze quantum interference and decoherence effects in single-molecule junctions both experimentally and theoretically by means of the mechanically controlled break junction technique and density-functional theory. We consider the case where interference is provided by overlapping quasi-degenerate states. Decoherence mechanisms arising from the electronic-vibrational coupling strongly affect the electrical current flowing through a single-molecule contact and can be controlled by temperature variation. Our findings underline the all-important relevance of vibrations for understanding charge transport through molecular junctions.Comment: 5 pages, 4 figure

Strategic modification of ligands for remarkable piezochromic luminescence (PCL) based on a neutral Ir(iii) phosphor

A new aggregation-induced emission (AIE)-active neutral Ir(III) complex has been rationally designed and synthesized by introducing carboxyl and F substituents into the ancillary and cyclometalating ligands, respectively, to construct different kinds of intermolecular interaction, leading to excellent piezochromic luminescence (PCL) properties. The emission colours are tunable by a grinding–fuming/heating process with good reversibility in the solid state. A combination of powder X-ray diffraction, differential scanning calorimetry, 1H NMR, X-ray photoelectron and Fourier-transform infrared spectroscopy unambiguously confirm that the mechanism of PCL involves disruption of the intermolecular π–π interactions and hydrogen bonding. The combined AIE and PCL properties have enabled an efficient re-writable data recording device to be fabricated using the Ir(III) complex as the active material

A study of planar anchor groups for graphene-based single-molecule electronics

To identify families of stable planar anchor groups for use in single molecule electronics, we report detailed results for the binding energies of two families of anthracene and pyrene derivatives adsorbed onto graphene. We find that all the selected derivatives functionalized with either electron donating or electron accepting substituents bind more strongly to graphene than the parent non-functionalized anthracene or pyrene. The binding energy is sensitive to the detailed atomic alignment of substituent groups over the graphene substrate leading to larger than expected binding energies for –OH and –CN derivatives. Furthermore, the ordering of the binding energies within the anthracene and pyrene series does not simply follow the electron affinities of the substituents. Energy barriers to rotation or displacement on the graphene surface are much lower than binding energies for adsorption and therefore at room temperature, although the molecules are bound to the graphene, they are almost free to move along the graphene surface. Binding energies can be increased by incorporating electrically inert side chains and are sensitive to the conformation of such chains

Osteoma Cutis Associated with Nevus Sebaceus: Case Report and Review of Cutaneous Osteoma-associated Skin Tumors (COASTs)

Osteoma cutis is a benign cutaneous lesion characterized by the presence of bone within the dermis or subcutaneous fat. It most often develops in association with other skin lesions such as cutaneous tumors. Nevus sebaceus is a benign hamartoma of the skin that is composed of epidermal and dermal components. It most commonly appears on the scalp and may give rise to either benign or malignant secondary neoplasms. The clinical and pathologic features of a 36-year-old man with a nevus sebaceus and associated osteoma cutis are described. In addition, osteoma cutis-associated neoplasms are reviewed. Secondary osteoma cutis has been observed with both benign and malignant neoplasms as well as various non-neoplastic skin conditions. However, to the best of our knowledge, osteoma cutis has not previously been described in association with nevus sebaceus. Nevus sebaceus can now be added to the list of cutaneous osteoma-associated skin tumors (COASTs)

Recent Progress in Nonconventional Luminescent Macromolecules and their Applications

Traditional π-conjugated luminescent macromolecules typically suffer from aggregation-caused quenching (ACQ) and high cytotoxicity, and they require complex synthetic processes. In contrast, nonconventional luminescent macromolecules (NCLMs) with nonconjugated structures possess excellent biocompatibility, ease of preparation, unique luminescence behavior, and emerging applications in optoelectronics, biology, and medicine. NCLMs are currently believed to produce inherent luminescence due to through-space conjugation of overlapping electron orbitals in solid/aggregate states. However, as experimental facts continue to exceed expectations or even overturn some previous assumptions, there is still controversy about the detailed luminous mechanism of NCLMs, and extensive studies are needed to further explore the mechanism. This Perspective highlights recent progress in NCLMs and classifies and summarizes these advances from the viewpoint of molecular design, mechanism exploration, applications, and challenges and prospects. The aim is to provide guidance and inspiration for the huge fundamental and practical potential of NCLMs

Structural Diversity in Cyclometalated Diiridium(III) Complexes with Bridging syn and anti μ2‐Oxamidato and μ2‐Dithioxamidato Ligands

Six new diiridium complexes containing 2-methyl-6-phenylpyridyl as the cyclometalating ligand with a μ2-oxamidato or a μ2-dithioxamidato ligand as the bridge have been synthesized in 60–73 % yields. These complexes were revealed by multinuclear NMR spectroscopy to contain inseparable mixtures of diastereomers (rac, ΔΔ/ΛΛ and meso, ΔΛ) with bridges in anti and syn configurations. The remarkable variety of isomers present was confirmed by X-ray crystallography on single crystals grown from mixtures of each complex. In one complex with a N,N’-bis(4-trifluoromethylphenyl)-μ2-oxamidato bridge, two single crystals of anti and syn isomers were structurally determined. Two single crystals of the μ2-dithioxamidato bridge complex were found to contain rac and meso forms of the syn isomer. Hybrid DFT computations on the four isomers of each diiridium complex revealed negligible energetic preferences for one isomer despite the methyl groups in the 2-methyl-6-phenylpyridyl cyclometalating ligands being close to the neighboring methyl groups and the bridge, thus supporting the experimental findings of isomer mixtures. Two distinct broad emissions with maxima at 522–529 nm and at 689–701 nm observed in these complexes in dichloromethane are attributed to mixed metal-ligand to ligand charge transfer (MLLCT) excited states involving the pyridyl and bridge moieties respectively with the aid of electronic structure computations