A series of 2-(1-benzyl-2-(styryl)-6-methylpyridin-4(1H)-ylidene) fragment containing glassy organic compounds have been synthesized from relevant luminescent 4H-pyran-4-ylidene derivatives and investigated as potential solution processable emitters. Glass transition temperatures of synthesized 1H-pyridine compounds are above 100°C with thermal stabilities higher than 260°C. In the solutions of dichloromethane their absorption bands are in the range from 350 nm to 500 nm with photoluminescence from 500 nm to 650 nm. In a contrary to the 4H-pyran-4-ylidene derivatives, the incorporation of various electron acceptor fragments within the 1H-pyridine fragment containing molecules only slightly influenced absorption and photoluminescence band shifts. Based on these compounds, neat spin-cast films were obtained and investigated as light-emitting mediums which show amplified spontaneous emission (ASE) with λmax in the range from 603 nm to 615 nm with ASE threshold values as low as 46 μJ/cm2. Synthesized 1H-pyridine derivatives show perspective to be applied as solution-processable components for light-amplification studies.
A series of 2,6-bis-styryl-4H-pyran-4-ylidene fragment containing glass-forming organic compounds with bonded amorphous phase promoting bulky triphenyl moieties through piperazine structural fragment [2-(2-(4-(bis(2-(trityloxy)ethyl)amino)styryl)-6-methyl-4H-pyran-4ylidene)malononitrile derivatives (DWK)-T dyes] in a form of (5,5,5-triphenylpentyl)piperazin-1-yl)styryl)-substituent attached to the 4H-pyran-4-yliden fragment in two-position have been synthesized and investigated as the potential light-amplification medium for organic solid-state lasers. DWK-T dye physical properties also depend on the structure of the other styryl-substituent attached to the 4H-pyran-4-ylidene backbone fragment in six-position. Thermal stability of synthesized dyes is above 312°C with the glass transitions from 97°C and up to 109°C. Obtained neat pure spin-cast films based on these compounds show photoluminescence with λmax in range from 672 to 695 nm, ASE λmax from 690 to 704 nm with ASE threshold values in range from 327 to 1091 μJ / cm2, which are mostly influenced by the nature of the electron transition characteristics of various four substituents in a 6-styryl-fragment. The proposed synthetic approach could be useful for obtaining chemically stable and covalently bonded bulky triphenyl group containing glassy dyes, while the synthetic design allows to acquire different nonsymmetric 2,6-bis-styryl-4H-pyran-4-ylidene fragment-containing compounds for red and infrared light-emitting and light amplification applications.
In this work photoluminescence and amplified spontaneous emission properties of new original 2-cyanoacetic acid derivative in different concentration mixed in polyvinyl carbazole (PVK) matrix were investigated. Ethyl 2-(2-(4-(bis(2- (trityloxy)ethyl)amino)styryl)-6-tert-butyl-4H-pyran-4-ylidene)-2-cyanoacetate (KTB) is recently synthesised nonsymmetric red light emitting laser dye, that in previous experiments with neat thin films showed low amplified spontaneous emission (ASE) threshold value. Based on PVK high refractive index it has been used as a polymer to ensure the preparation of good planar waveguide. Luminescence quenching is expected in neat amorphous thin films according to previous experiments which reduces photoluminescence quantum yield and increases ASE excitation threshold energy. It could be overcome by a decrease of the intermolecular interactions between laser active molecules by doping them in polymer matrix thereby decreasing photoluminescence quenching effect in the system by increasing distance between organic molecules which in turn results in lowering ASE excitation threshold energy. The lowest threshold value of ASE was achieved at 20wt% of KTB molecule in PVK matrix. Ability to significantly decrease intermolecular interactions and excitation threshold energy of investigated compound in host-guest systems makes it promising to be used as a laser dye in preparation of organic solid state lasers.
During the last two decades, small organic molecules have been widely studied for potential applications in organic solid-state lasers due to low-cost production, simple processing possibility and physical property tuning ability through chemical structure synthetic modifications. One of the most investigated and applied compound in dye lasers is 4- (dicyanomethylene)-2-methyl-6-(4-dimethylaminostyryl)-4H-pyran (DCM). It has shown remarkable properties as a dye in solid-state lasers. One of the drawbacks of this compound is high intermolecular interactions which reduce emission efficiency. Therefore it can be applied only in doped systems in low concentration (around 2 wt%). Recently we have demonstrated that incorporation of bulky triphenyl groups in the low molecular mass organic compounds enables the ability to form good optical quality transparent glassy films by solution processing. Additional such bulky groups reduce intermolecular interaction thus increase photoluminescence quantum yield in the thin film. In the presentation, we will show optical properties of new 2-cyanoacetic derivatives where two different bulky groups (9H-carbazole fragment and triphenyl group) are attached to molecule electron donating and accepting parts. Synthesized compounds have light absorption from 400nm to 600nm and photoluminescence from 600 nm up to 800 nm. Dyes with only one incorporated electron donating fragment showed 16% PLQY and ASE excitation threshold values (below 52 μJ/cm2) in neat thin films. Two electron donating fragment containing molecules have PLQY of 7% and ASE excitation threshold 223 μJ/cm2.
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