Substituent-Controlled Photophysical Responses in Dihydropyridine Derivatives and Their Application in the Detection of Volatile Organic Contaminants.

In the ever-expanding realm of organic fluorophores, structurally simple and synthetically straightforward molecules with unique photophysical properties have received special attention. Among these, 1,4-dihydropyridine (DHP) is an important scaffold that permits fine-tuning of their photophysical properties through substituents on the periphery. Herein, we describe a series of solid-emissive N-substituted 2,6-dimethyl-4-methylene-1,4-dihydropyridine derivatives appended with electron-withdrawing substituents (dicyanomethylene or 2-dicyanomethylene-3-cyano-2,5-dihydrofuran) at the C-4 position and alkyl or alkylaryl groups on the DHP nitrogen. Electronic and steric tuning exerted by these substituents resulted in interesting photophysical properties such as negative solvatochromism, solidstate, and aggregation-induced emission (AIE). Theoretical calculations were carried out to explain the solvatochromic properties. Insight into the AIE properties was obtained through variable-temperature nuclear magnetic resonance and viscosity- and temperature-dependent emission studies. The variations in molecular packing in the crystal lattice with changes in the N-substituents contributed to the tuning of solid state emission properties. Detection of aromatic volatile organic compounds (VOCs) was achieved using the aggregates of the DHP derivatives. Among the VOCs, p-xylene elicited a significant enhancement in emission, allowing its detection at submicromolar levels.

Photokinetic study on remarkable excimer phosphorescence from heteroleptic cyclometalated platinum(ii) complexes bearing a benzoylated 2-phenylpyridinate ligand.

Novel heteroleptic cyclometalated platinum(ii) complexes consisting of 5'-benzoylated 2-phenylpyridinate (ppy) cyclometalated and acetylacetonate ancillary ligands were synthesized, and their photoluminescence (PL) properties were investigated. The 5'-benzoylated complex without any other substituents exhibited phosphorescence-based monomer emission at 479 nm in dichloromethane (10 µM, rt) with a PL quantum yield of 0.28. On the other hand, in poly(methyl methacrylate) (PMMA) film, remarkable excimer emission additionally emerged at ca. 600 nm with a relatively high PL quantum yield of 0.47 as the doping level increased to 0.20 mmmol g-1, which was comparably intense in comparison with the monomer emission. In the case of the complexes with unsubstituted, 4'-benzoylated, and 5'-fluorinated ppy cyclometalated ligands, excimer emission was modestly generated at the same doping level, and thus the introduction of a benzoyl group to the 5'-position is effective to obtain remarkable excimer emission. The combination of benzoyl and fluoro groups was more effective at inducing excimer emission, and the intensity of excimer emission of the 2-(5-benzoyl-4,6-difluorophenyl)pyridinate-based complex was 3.5 times larger than that of monomer emission at a doping level of 0.20 mmmol g-1 in PMMA. From the analysis of PL lifetimes at varying concentrations, photokinetic profiles were fully analyzed according to the model system for the irreversible excimer formation, and the excimer formation rate constant of the 5'-benzoylated complex was determined in dichloromethane as 2.2 × 109 M-1 s-1, which is 4.4 times larger than that of the unsubstituted complex. We also fabricated an organic light-emitting diode using the 2-(5-benzoyl-4,6-difluorophenyl)pyridinate-based complex as a single emitter. The device exhibited pseudo-white EL with the Commission internationale de l'éclairage chromaticity coordinates of (0.42, 0.42).

Effect of the electric field during annealing of organic light emitting diodes for improving its on/off ratio.

If an organic light emitting diode is to be used as part of a matrix addressed array, it should exhibit low reverse leakage current. In this paper we present a method to improve the on/off ratio of such a diode by simultaneous application of heat and electric field post device fabrication. A green OLED with excellent current efficiency was seen to be suffering from a poor on/off ratio of 10(2). After examining several combinations of annealing along with the application of a reverse bias voltage, the on/off ratio of the same device could be increased by three orders of magnitude, specifically when the device was annealed at 80 °C under reverse bias (-15 V) followed by slow cooling also under the same bias. Simultaneously, the forward characteristics of the device were relatively unaffected. The reverse leakage in the OLED is mainly due to the injection of minority carriers in the hole transport layer (HTL) and the electron transport layer (ETL), in this case, of holes in tris-(8-hydroxyquinoline)aluminum(Alq3) and electrons in 4,4',4''-tris(N-3-methylphenyl-N-phenylamino)triphenylamine (m-MTDATA). Hence, to investigate these layers adjacent to the electrodes, we fabricated their single layer devices. The possibility of bulk traps present adjacent to electrodes providing states for injection was ruled out after estimating the trap density both before and after the reverse biased annealing. The temperature independent current in reverse bias ruled out the possibility of thermionic injection. The origin of the reverse bias current is attributed to the availability of interfacial hole levels in Alq3 at the cathode work function level in the as-fabricated device; the suppression of the same being attributed to the fact that these levels in Alq3 are partly removed after annealing under an electric field.

Thermally Activated Delayed Fluorescent Solvent-free Organic Liquid Hybrids for Tunable Emission Applications.

The synthetic feasibility and excellent luminescence features of organic molecules attracted much attention and were eventually found useful in lighting applications. In this context, a solvent-free organic liquid having attractive thermally activated delayed fluorescence features in bulk along with high processability has prime importance. Herein, we report a series of naphthalene monoimide-based solvent-free organic liquids exhibiting cyan to red thermally activated delayed fluorescence with luminescence quantum yields up to 80% and lifetimes between 10 to 45 µs. An effective approach explored energy transfer between liquid donors with various emitters exhibiting tunable emission colors, including white. The high processability of liquid emitters improved the compatibility with polylactic acid and was used for developing multicolor emissive objects using 3D printing. Our demonstration of the thermally activated delayed fluorescence liquid will be much appreciated as a processable alternate emissive material suitable for large-area lighting, display, and related applications.