Triphenyl moieties as building blocks for obtaining molecular glasses with nonlinear optical activity
The incorporation of trityl and triphenylsilyl groups into low molecular weight molecules allows the formation of stable molecular glasses. A series of materials based on the N-phenyldiethanolamine core was synthesized bearing different azobenzenes and benzylydene-1,3-indandione as active chromophores. Molecular hyperpolarizability of the synthesized compounds was calculated by a restricted Hartree–Fock method with basis 6-31G(d,p) and measured in solutions by hyper-Rayleigh scattering. Non-linear optical (NLO) activity of the thin glassy films was confirmed after a corona poling procedure. Thermal sustainability of the NLO response of up to 85 °C was achieved. Quantum chemical calculations…
Perovskite CH3NH3PbI3–XClx Solar Cells. Experimental Study of Initial Degradation Kinetics and Fill Factor Spectral Dependence
The main drawback of the methylammonium lead halide perovskite solar cells is their degradation in ambient atmosphere. To investigate ambient-air-induced cell degradation, spec-tral dependencies of open-circuit voltage (VOC), fill factor (FF) and the power conversion effi-ciency (PCE) have been acquired (for the first time reported in literature). Our custom-made measurement system allowed us to perform measurements of the above-mentioned entities in situ directly in vacuum during and after thermal deposition of the elec-trode. We also studied how these parameters in vacuum changed after cell exposure to ambient air for 85 min (50 nm top electrode) and for 180 min (100 nm top Ag electrode).…
Determination of Kerr and two-photon absorption coefficients of indandione derivatives
This material is based upon work supported by the ERDF 1.1.1.1 activity project Nr. 1.1.1.1/16/A/046 “Application assessment of novel organic materials by prototyping of photonic devices” as well as by National Research Program “Multifunctional Materials and Composites, Photonics and Nanotechnology” (IMIS2) project “Photonics and materials for photonics”.
Stereoselective synthesis and properties of 1,3-bis(dicyanomethylidene)indane-5-carboxylic acid acceptor fragment containing nonlinear optical chromophores
A series of organic push–pull type chromophores using indane-1,3-dione 5-carboxylic acid (IDCA) and novel 1,3-bis(dicyanomethylidene)indane 5-carboxylic acid (CICA) electron acceptor fragments have been synthesized and characterized. NMR and X-ray analysis revealed that condensation reactions with the CICA fragment were stereoselective and yielded benzylidenes and azomethines with E double bond configurations. Due to the non-planar geometry these compounds are chiral and were acquired as a racemic mixture. The subsequent functionalization of the carboxylic acid group with 5,5,5-triphenylpentan-1-ol yielded solution-processable glass forming materials (6, 8, 10, 13) with glass transition tem…
Hyper-Rayleigh scattering and two-photon luminescence of phenylamine- indandione chromophores
Based on results of quantum chemical (QC) screening, we put under research several phenylamine indane-1,3-dione derivatives including octupolar NLO chromophore A3BI. According to these calculations, molecular first hyperpolarizability (βHRS) should be enhanced upon replacement of methyl substituents with phenyl groups. Surprisingly, βHRS values obtained in our measurements by hyper-Rayleigh scattering (HRS) are much higher than one could expect from QC. Bearing in mind that two-photon luminescence (TPL) is usual cause for overestimation of βHRS in HRS measurements, we have accomplished investigations of TPL properties of these compounds. All investigated triphenylamine derivatives exhibit s…
Origin of Kerr effect: investigation of solutions by polarization dependent Z-scan
This material is based upon work supported by the ERDF 1.1.1.1 activity project No. 1.1.1.1/16/A/046 “Application assessment of novel organic materials by prototyping of photonic devices”.
Rational computing of energy levels for organic electronics: the case of 2-benzylidene-1,3-indandiones
Device engineering in organic electronics, an active area of research, requires knowledge of the energy levels of organic materials (traditionally but ambiguously denoted as HOMO and LUMO). These can be effectively determined by electrochemical investigation, but yet more effective would be quantum chemical (QC) computation of these quantities. However, there is no consensus on the computational method in the research community. Ongoing discussions often focus on choosing the right density functional method, but neglect other model parameters, in particular, the basis set. This study considers comparison of various methodologies and parameters for predicting ionization energy I and electron…
Donor and acceptor substituted triphenylamines exhibiting bipolar charge-transporting and NLO properties
Donor-acceptor type triphenylamine-based malonodinitriles were synthesized and their thermal, optical, photophysical, electrochemical and nonlinear optical properties were studied. The synthesized compounds formed glasses with the glass transition temperatures ranging from 38 to 107 °C. The ionization potentials of the samples of the compounds established by cyclic voltammetry were found to be in the range of 5.50–5.57 eV, while those estimated by photoelectron emission spectrometry ranged from 5.36 to 5.74 eV. The electron affinity values of the compounds were found to be in the range of −3.41–−3.05 eV. The ambipolar charge-transporting properties were observed for the layers of triphenyla…
Study of Structure–Third-Order Susceptibility Relation of Indandione Derivatives
By using the Z-scan method we studied the third-order nonlinear optical parameters of several aminobenziliden-1,3-indandione (ABI) derivatives that have previously been shown to own second-order nonlinear optical properties. Measurements were carried out using two 1064 nm Nd:YAG lasers with picosecond (ps) and nanosecond (ns) pulse widths, respectively. When ns laser was employed in the Z-scan setup, a strong thermal lensing took place resulting in severe overestimation of optical Kerr coefficients. Due to this reason the ps laser was employed to evaluate correct magnitude of Kerr effect. For investigated organic molecules, experimental results show that two-photon absorption at 1064 nm is …
Unusual response to environmental polarity in a nonlinear-optical benzylidene-type chromophore containing a 1,3-bis(dicyanomethylidene)indane acceptor fragment.
One of the strongest known electron-accepting fragments used in the synthesis of organic dyes for applications in nonlinear optics (NLO) is 1,3-bis(dicyanomethylidene)indane (BDMI). By studying a benzylidene-type push-pull chromophore bearing a 5-carboxy-BDMI electron-acceptor and 4-(dimethylamino)aniline donor fragment, we demonstrate that this class of compounds can show unusual response to the polarity of the surrounding medium. The combined results of UV-Vis absorption spectrometry, NMR experiments and computational modeling indicate that the studied compound undergoes a geometrical transformation that involves an increase in the torsion angle ω between the aniline and indane ring syste…
Synthesis and thermoelectric properties of 2- and 2,8-substituted tetrathiotetracenes
Reaction of elemental sulfur with 2-R1 and 2,8-R1,R2-substituted tetracenes (2) in refluxing DMF affords 5,6,11,12 tetrathiotetracenes (1) in good yields (74–99%) for a range of substituents where R1,R2 are: H,H (a); Me,H (b); MeO,H (c); Ph,H (d); Me,Me (e), iPr,Me (f, iPr = iso-propyl, CHMe2), Me,MeO (g); MeO,MeO (h). The reaction rate is limited only by the solubility of the tetracene (2); 2g–h being both the least soluble and slowest reacting. At partial conversion recovered single crystalline 2g led to its X-ray structure determination. Vacuum deposited (substrate deposition temperature 300 K, pressure 7 × 10−6 mbar, source temperature 500 K) thin films from 1 (of initial 88–99% purity)…
An improved molecular design of obtaining NLO active molecular glasses using triphenyl moieties as amorphous phase formation enhancers
New molecular design of obtaining molecular glasses has been developed by linking triphenylmethyl moieties to chromophore core by flexible C-C bridge. Compounds capable of forming stable amorphous phase with good optical quality have been acquired with increased chemical and thermal sustainability compared to the previously reported design. NLO activity of compounds has been measured after corona discharge polling. Compared to previously synthesized trityloxy fragment containing compounds increase of d 33 coefficient by up to 17 times was achieved for the same chromophore core containing compounds.
Synthesis and nonlinear optical properties of novel N,N-dihydroxyethyl-based molecular organic glasses using triaryl substitutes as amorphous phase formation enhancers
In given study a new structural design of molecular NLO materials is presented where amorphous phase formation is achieved by introduction of bulky trityl and triphenylsilyl substituents. Obtained materials formed stable organic glasses with good optical quality and glass transition temperatures notably exceeding ambient. NLO activity was successfully measured in samples that underwent corona discharge poling. The comparison of both enhancer groups revealed, that trityl group increases thermal sustainability of material, while triphenylsilyl group better promotes formation and stability of amorphous phase.
Perovskite CH3NH3PbI3–XClx Solar Cells and their Degradation (Part 1: A Short Review)
Development of hybrid organic-inorganic perovskite solar cells (PSC) has been one of the hottest research topics since 2013. Within brief literature review, we would like to achieve two objectives. Firstly, we would like to indicate that a whole set of physical properties, such as high change carrier mobility, very low recombination rates, large carrier life time and diffu-sion length, large absorption coefficients and very weak exciton binding energies, are defining high power conversion efficiency (PCE) of methyl ammonium lead trihalide SC. The second objective is to draw attention to some, in our opinion, important aspects that previously have not been satisfactory addressed in literatur…
Emission Enhancement by Intramolecular Stacking between Heteroleptic Iridium(III) Complex and Flexibly Bridged Aromatic Pendant Group
Phosphorescent iridium(III) complexes suffer from a strong aggregation quenching, limiting their use in solution-processed or crystalline organic light-emitting diodes. Here we report how an intramolecular stacking between a flexibly bridged bulky aromatic pendant group and the core of nonionic heteroleptic complex can be exploited to minimize the negative effects of this drawback. The stacked conformation provides a rigid sterical shielding of the polar molecular surface, improving photoluminescence quantum yield of the complex both in solution and crystalline state.
Thiphenylmethane based structural fragments as building blocks towards solution-processable heteroleptic iridium(iii) complexes for OLED use
A novel structural approach to solution-processable heteroleptic iridium(III) complexes is presented. On the basis of 2-arylbenzo[d]thiazole cyclometalating main ligands and picolinic acid (pic) and acetylacetone (acac) ancillary ligands six new yellow or orange emitting materials were obtained using attached 1,1,1-triphenylmethylpentane substituents as aggregation preventing and solubility enhancing functional fragments. The obtained compounds show high photoluminescence quantum yield values in the range of 0.64 to 0.90. OLEDs with a spin-coated emissive layer were successfully prepared, with the highest achieved external quantum efficiency of 7.9%, current efficiency of 12.4 cd A−1 and po…
CCDC 1845861: Experimental Crystal Structure Determination
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CCDC 1436954: Experimental Crystal Structure Determination
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CCDC 1811026: Experimental Crystal Structure Determination
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