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The optimization of dye-sensitized solar cells (DSSCs) technology towards suppressing charge recombination between the contact and the electron transport layer is a key factor in achieving high conversion efficiency and the successful commercialization of this type of product. An important aspect of the DSSC structure is the front blocking layer (BL): optimizing this component may increase the efficiency of photoelectron transfer from the dye to the semiconductor by reduction charge recombination at the TiO2/electrolyte and FTO/electrolyte interfaces. In this paper, a series of blocking layer variants, based on TiO2 and ZnO:TiO2, were obtained using the reactive magnetron sputtering method. Material composition, structure and layer thickness were referred to each process parameters. Complete DSSCs with structure FTO/BL/m-TiO2@N719/ EL-HSE/Pt/FTO were obtained on such bases. In the final results, verification of opto-electrical parameters of these cells were tested and used for the conclusions on the optimal blocking layer composition. As the conclusion, application of blocking layer consists of neat TiO2 resulted in improvement of device efficiency. It should be noted that for TiO2:ZnO/CuxO and TiO2/CuxO cells, higher efficiencies were also achieved when pure TiO2 was used as window layer. Additionally it was proven that the admixture of ZnO phase inspires Voc and FF growth, but is overall unfavorable compared to pristine TiO2 blocking layer and the reference cell, according to the final cell efficiency.
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A new azo polymer containing photoisomerizable azo pyridine functionalities was synthesized via Mitsunobu reaction of 4-(4-hydroxyphenylazo)pyridine with poly(2-hydroxyethyl methacrylate-co-methyl methacrylate) (p(HEMA-co-MMA)) for creating new photochromic materials. The resulting polymer with azo pyridine side groups was characterized for structural, thermal, and optical properties. UV-vis, 1H NMR and IR spectroscopies confirmed that all hydroxyl groups in p(HEMA-co-MMA) were substituted with azo dye. The obtained azo copolymer exhibited high thermal stability (around 240 °C) and a glass transition temperature (113 °C), promising for applications. The trans-to-cis isomerization upon UV irradiation and the thermal back reaction of the azo chromophore in the copolymer in the solid state was studied. A photostationary state with 50% content of cis-isomers upon 6 min of UV irradiation was reached, and during 48 h dark relaxation at ambient temperature, all cis-isomers converted to the trans form. Additionally, the possibility of efficient photogeneration of surface relief gratings with high amplitude of azo copolymer surface modulation was demonstrated.
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The seven N-phthalimide derivatives substituted with the amine group at the 3-C position in the phenylene ring were synthesized. The effect of N-substituent chemical structure was investigated. The thermal, electrochemical and optical studies were performed and supported by the density functional theory calculations (DFT). The electrochemical investigations of the synthesized low-molecular phthalimides revealed the one oxidation and reduction process with the HOMO energy level under - 5.81 eV and energy-band gap below 3 eV. The N-phthalimide derivatives were emitted light in a blue spectral region in solutions (in polar and non-polar) with the quantum yield between 2 and 68%, dependent on the substituent at the nitrogen atom, solvent and concentration. The N-phthalimide derivatives were emissive also in a solid state as a thin film and powder. They were tested as a component of the active layer with PVK:PBD matrix and as an independent active layer in the organic light-emitting diodes. The registered electroluminescence spectra exhibited the maximum emission band in the 469-505 nm range, confirming the possibility of using N-phthalimides with PVK:PBD matrix as the blue emitters.
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Fluorene-based low molar weight derivatives were synthesized in Suzuki reactions by using key starting materials 9-benzylidene-2,7-dibromofluorene or 3-(2,7-dibromofluoren-9-ylmethylen)-9-ethylcarbazole and various aryl boronic acids. Photophysical properties of the compounds were investigated in different solutions as well as in solid state. The thermal investigations showed that the obtained compounds are highly thermally stable with temperatures of 5% mass loss (T5%) in the range of 311-432 °C. Some of the compounds also exhibited very high glass transition temperatures exceeding 125 °C. The presented molecules were electrochemically active and showed the energy band gap below 2.97 eV. The investigations were supported by DFT calculations and the photovoltaic ability of the presented compounds was tested in the organic-inorganic solar cells.
Asunto(s)
Ácidos Borónicos , Fluorenos , Teoría Funcional de la Densidad , Modelos TeóricosRESUMEN
Among light-responsive materials for photonics, azo polymers occupy an important position due to their optical response and the related concepts of consecutive applications. However, scientific insight is still needed to understand the effects of irradiation on the modification of the azo polymer structure and the effect of this modification on incoming probing light. In this work, we report on a surface relief grating with a maximum depth of a record-high value of 1.7 µm, inscribed holographically in a custom synthesized glassy azo polymer belonging to the poly(ether imide) family. We show that the specifically deformed polymer, forming an amplitude-modulated relief grating, has a unique dual effect on an incoming light beam of different diameters. When illuminated by a narrow probe beam, the structure acts as a variable-depth grating, enabling a continuous tuning of the diffraction efficiencies in the entire theoretically predicted range and, thus, generating or eliminating diffracted waves of specified order. Alternatively, when illuminated by a wide probe beam, the whole structure acts as an optical component reshaping the Gaussian light intensity profile into the profiles resembling the squares of Bessel functions of the zeroth- or higher orders. Moreover, a physical justification of the effects observed is provided.
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In this research, six novel unsymmetrical imino-1,8-naphthalimides (AzNI) were synthesized. Comprehensive thermal (thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC), optical (UV-Vis, photoluminescence), and electrochemical (CV, DPV) studies were carried out to characterize these new compounds. The molecules showed the onset of thermal decomposition in the temperature range 283-372 °C and molecular glass behavior. Imino-1,8-naphthalimides underwent reduction and oxidation processes with the electrochemical energy band gap (Eg) below 2.41 eV. The optical properties were evaluated in solvents with different polarities and in the solid-state as a thin films and binary blends with poly(N-vinylcarbazole): (2-tert-butylphenyl-5-biphenyl-1,3,4-oxadiazole) (PVK:PBD). Presented compounds emitted blue light in the solutions and in the green or violet spectral range in the solid-state. Their ability to emit light under external voltage was examined. The devices with guest-host structure emitted light with the maximum located in the blue to red spectral range of the electroluminescence band (EL) depending on the content of the AzNI in the PVK:PBD matrix (guest-host structure).
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The structure-property correlations and control of electronic excited states in transition metal complexes (TMCs) are of high significance for TMC-based functional material development. Within these studies, a series of Re(I) carbonyl complexes with aryl-substituted 2,6-di(thiazol-2-yl)pyridines (Arn-dtpy) was synthesized, and their ground- and excited-state properties were investigated. A number of condensed aromatic rings, which function as the linking mode of the aryl substituent, play a fundamental role in controlling photophysics of the resulting [ReCl(CO)3(Arn-dtpy-κ2N)]. Photoexcitation of [ReCl(CO)3(Arn-dtpy-κ2N)] with 1-naphthyl-, 2-naphthyl-, 9-phenanthrenyl leads to the population of 3MLCT. The lowest triplet state of Re(I) chromophores bearing 9-anthryl, 2-anthryl, 1-pyrenyl groups is ligand localized. The rhenium(I) complex with appended 1-pyrenyl group features long-lived room temperature emission attributed to the equilibrium between 3MLCT and 3IL/3ILCT. The excited-state dynamics in complexes [ReCl(CO)3(9-anthryl-dtpy-κ2N)] and [ReCl(CO)3(2-anthryl-dtpy-κ2N)] is strongly dependent on the electronic coupling between anthracene and {ReCl(CO)3(dtpy-κ2N)}. Less steric hindrance between the chromophores in [ReCl(CO)3(2-anthryl-dtpy-κ2N)] is responsible for the faster formation of 3IL/3ILCT and larger contribution of 3ILCTanthraceneâdtpy in relation to the isomeric complex [ReCl(CO)3(9-anthryl-dtpy-κ2N)]. In agreement with stronger electronic communication between the aryl and Re(I) coordination centre, [ReCl(CO)3(2-anthryl-dtpy-κ2N)] displays room-temperature emission contributed to by 3MLCT and 3ILanthracene/3ILCTanthraceneâdtpy phosphorescence. The latter presents rarely observed phenomena in luminescent metal complexes.
Asunto(s)
Complejos de Coordinación , Renio , Antracenos , Ligandos , PiridinasRESUMEN
Three new azomethines based on triphenylamine with two or three substituents were obtained. Chemical structure and purity were confirmed by 1H NMR, FTIR elemental analysis and mass spectroscopy. The investigations were focused on the relationship between chemical structure and properties important for optoelectronic materials. Thus, the studies of thermal, optical and electrochemical properties were carried out based on differential scanning calorimetry, thermogravimetric analysis, electronic absorption, photoluminescence and cyclic voltammetry measurements. The ongoing consideration of experimental results was complemented by theoretical calculations using the density functional theory method. The donor activity of obtained compounds was tested in bulk-heterojuntion photovoltaic cells with structure ITO/PEDOT:PSS/imine:PCBM/Al and ITO/PEDOT:PSS/imine:P3HT:PCBM/Al). The effect of the presence of the amino-thiophene-3,4-dicarboxylic acid diethyl ester groups and various number of hexyloxyphenyl units on imines properties was demonstrated.
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Rhenium(I) complexes with 2,2':6',2â³-terpyridines (terpy) substituted with 9-anthryl (1) and 2-anthryl (2) were synthesized, and the impact of the anthryl linking mode on the ground- and excited-state properties of resulting complexes [ReCl(CO)3(4'-An-terpy-κ2N)] (Anâanthryl) was investigated using a combination of steady-state and time-resolved optical techniques accompanied by theoretical calculations. Different attachment positions of anthracene modify the overlap between the molecular orbitals and thus the electronic coupling of the anthracene and {ReCl(CO)3(terpy-κ2N)} chromophores. Following the femtosecond transient absorption, the lowest triplet excited state of both complexes was found to be localized on the anthracene chromophore. The striking difference between 1 and 2 concerns the triplet-state formation dynamics. A more planar geometry of 2-anthryl-terpy (2), and thus better electronic communication between the anthracene and {ReCl(CO)3(terpy-κ2N)} chromophores, facilitates the formation of the 3An triplet state. In steady-state photoluminescence spectra, the population ratio of 3MLCT and 3An was found to be dependent not only on the anthryl linking mode but also on solvent polarity and excitation wavelengths. In dimethyl sulfoxide (DMSO), compounds 1 and 2 excited with λexc > 410 nm show both 3MLCT and 3An emissions, which are rarely observed. Additionally, the abilities of the designed complexes for 1O2 generation and light emission under the external voltage were preliminary examined.
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A new series of thiophene-based azomethines differing in the core structure was synthesized. The effect of the central core structure in azomethines on the thermal, optical and electrochemical properties was investigated. The obtained compounds exhibited the ability to form a stable amorphous phase with a high glass transition temperature above 100 °C. They were electrochemically active and undergo oxidation and reduction processes. The highest occupied (HOMO) and the lowest unoccupied molecular (LUMO) orbitals were in the range of -3.86--3.60 eV and -5.46--5.17 eV, respectively, resulting in a very low energy band gap below 1.7 eV. Optical investigations were performed in the solvents with various polarity and in the solid state as a thin film deposited on a glass substrate. The synthesized imines absorbed radiation from 350 to 600 nm, depending on its structure and showed weak emission with a photoluminescence quantum yield below 2.5%. The photophysical investigations were supported by theoretical calculations using the density functional theory. The synthesized imines doped with lithium bis-(trifluoromethanesulfonyl)imide were examined as hole transporting materials (HTM) in hybrid inorganic-organic perovskite solar cells. It was found that both a volume of lithium salt and core imine structure significantly impact device performance. The best power conversion efficiency (PCE), being about 35-63% higher compared to other devices, exhibited cells based on the imine containing a core tiphenylamine unit.
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Ésteres , Tiofenos , Compuestos Azo , Iminas , Litio , Tiofenos/química , TiosemicarbazonasRESUMEN
The paper presents synthesis and characterization of nine new thiazolyl-(phenyldiazenyl)-2H-chromen-2-one dyes. The impact of substituent structure in thiazole ring in the synthesized azocoumarin derivatives on electrochemical properties, photoisomerization process and photovoltaic response was examined. The dyes were electrochemically active and undergo reduction and oxidation processes. They showed low electrochemically estimated energy band gap in the range of 1.71-2.13 eV. Photoisomerization process of the synthesized molecules was studied in various solvents such as ethanol, chloroform and N,N-dimethylformamide (DMF) upon the UV illumination. It was found that novel azodyes showed reversible trans-cis-trans isomerization and exhibited long thermal back to the trans form, that was even 7 days in DMF. Selected azocoumarin were molecularly dispersed in polystyrene for preparation of guest-host azopolymer systems to study the cis-trans thermal isomerization of obtained dyes in solid state. The photovoltaic activity of the azochromophores was tested in bulk-heterojunction solar cells. They acting as weak donors in device with structure ITO/PEDOT:PSS/dye:PC70BM/Al. No photovoltaic response of cells with azocoumarin derivatives bearing 4-fluorobenzene, 3,4-dichlorobenzene, or 4-(1-adamantyl) unit was found. Additionally, dye which showed the best activity was examined in three-component solar cells ITO/PEDOT:PSS/PTB7:PC70BM:dye/PFN/Al.
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Colorantes , Colorantes/química , Oxidación-ReducciónRESUMEN
In the current work, comprehensive photophysical and electrochemical studies were performed for eight rhenium(I) complexes incorporating 2,2':6',2â³-terpyridine (terpy) and 2,6-bis(pyrazin-2-yl)pyridine (dppy) with appended 1-naphthyl-, 2-naphthyl-, 9-phenanthrenyl, and 1-pyrenyl groups. Naphthyl and phenanthrenyl substituents marginally affected the energy of the MLCT absorption and emission bands, signaling a weak electronic coupling of the appended aryl group with the Re(I) center. The triplet MLCT state in these complexes is so low lying relative to the triplet 3ILaryl that the thermal population of the triplet excited state delocalized on the organic chromophore is ineffective. The attachment of the electron-rich pyrenyl group resulted in a noticeable red shift and a significant increase in molar absorption coefficients of the lowest energy absorption of the resulting Re(I) complexes due to the contribution of intraligand charge-transfer (ILCT) transitions occurring from the pyrenyl substituent to the terpy/dppy core. At 77 K, the excited states of [ReCl(CO)3(Ln-κ2N)] with 1-pyrenyl-functionalized ligands were found to have predominant 3ILpyrene/3ILCTpyreneâterpy character. The 3IL/3ILCT nature of the lowest energy excited state of [ReCl(CO)3(4'-(1-pyrenyl)-terpy-κ2N)] was also evidenced by nanosecond transient absorption and time-resolved emission spectroscopy. Enhanced room-temperature emission lifetimes of the complexes [ReCl(CO)3(Ln-κ2N)] with 1-pyrenyl-substituted ligands are indicative of the thermal activation between 3MLCT and 3IL/3ILCT excited states. Deactivation pathways occurring upon light excitation in [ReCl(CO)3(4'-(1-naphthyl)-terpy-κ2N)] and [ReCl(CO)3(4'-(1-pyrenyl)-terpy-κ2N)] were determined by femtosecond transient absorption studies.
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A new series of 1,8-naphtalimides containing an imine bond at the 3-position of the naphthalene ring was synthesized using 1H, 13C NMR, FTIR, and elementary analysis. The impact of the substituent in the imine linkage on the selected properties and bioimaging of the synthesized compounds was studied. They showed a melting temperature in the range of 120-164 °C and underwent thermal decomposition above 280 °C. Based on cyclic and differential pulse voltammetry, the electrochemical behavior of 1,8-naphtalimide derivatives was evaluated. The electrochemical reduction and oxidation processes were observed. The compounds were characterized by a low energy band gap (below 2.60 eV). Their photoluminescence activities were investigated in solution considering the solvent effect, in the aggregated and thin film, and a mixture of poly(N-vinylcarbazole) (PVK) and 2-tert-butylphenyl-5-biphenyl-1,3,4-oxadiazole (PBD) (50:50 wt.%). They demonstrated low emissions due to photoinduced electron transport (PET) occurring in the solution and aggregation, which caused photoluminescence quenching. Some of them exhibited light emission as thin films. They emitted light in the range of 495 to 535 nm, with photoluminescence quantum yield at 4%. Despite the significant overlapping of its absorption range with emission of the PVK:PBD, incomplete Förster energy transfer from the matrix to the luminophore was found. Moreover, its luminescence ability induced by external voltage was tested in the diode with guest-host configuration. The possibility of compound hydrolysis due to the presence of the imine bond was also discussed, which could be of importance in biological studies that evaluate 3-imino-1,8-naphatalimides as imaging tools and fluorescent materials for diagnostic applications and molecular bioimaging.
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Novel oxetane-functionalized derivatives were synthesized to find the impact of carbazole substituents, such as 1-naphtyl, 9-ethylcarbazole and 4-(diphenylamino)phenyl, on their thermal, photophysical and electrochemical properties. Additionally, to obtain the optimized ground-state geometry and distribution of the frontier molecular orbital energy levels, density functional theory (DFT) calculations were used. Thermal investigations showed that the obtained compounds are highly thermally stable up to 360 °C, as molecular glasses with glass transition temperatures in the range of 142-165 °C. UV-Vis and photoluminescence studies were performed in solvents of differing in polarity, in the solid state as a thin film on glass substrate, and in powders, and were supported by DFT calculations. They emitted radiation both in solution and in film with photoluminescence quantum yield from 4% to 87%. Cyclic voltammetry measurements revealed that the materials undergo an oxidation process. Next, the synthesized molecules were tested as hole transporting materials (HTM) in perovskite solar cells with the structure FTO/b-TiO2/m-TiO2/perovskite/HTM/Au, and photovoltaic parameters were compared with the reference device without the oxetane derivatives.
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New benzo[h]quinolin-10-ol derivatives with one or two 2-cyanoacrylic acid units were synthesized with a good yield in a one-step condensation reaction. Chemical structure and purity were confirmed using NMR spectroscopy and elemental analysis, respectively. The investigation of their thermal, electrochemical and optical properties was carried out based on differential scanning calorimetry, cyclic voltammetry, electronic absorption and photoluminescence measurements. The analysis of the optical, electrochemical and properties was supported by density functional theory studies. The synthesized molecules were applied in dye-sensitized solar cells as sensitizers and co-sensitizers with commercial N719. The thickness and surface morphology of prepared photoanodes was studied using optical, scanning electron and atomic force microscopes. Due to the utilization of benzo[h]quinolin-10-ol derivatives as co-sensitizers, the better photovoltaic performance of fabricated devices compared to a reference cell based on a neat N719 was demonstrated. Additionally, the effect of co-adsorbent chemical structure (cholic acid, deoxycholic acid and chenodeoxycholic acid) on DSSC efficiency was explained based on the density functional theory.
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In this paper, six novel symmetrical bis-(imino-1,8-naphthalimides) differing in core and N-substituent structure were synthesized, and their thermal (TGA, DSC), optical (UV-Vis, PL), electrochemical (DPV, CV) properties were evaluated. The compounds were stable to 280 °C and could be transferred into amorphous materials. Electrochemical investigations showed their ability to occur reductions and oxidations processes. They exhibited deep LUMO levels of about -3.22 eV and HOMO levels above -5.80 eV. The optical investigations were carried out in the solutions (polar and non-polar) and in films and blends with PVK:PBD. Bis-(imino-1,8-naphthalimides) absorbed electromagnetic radiation in the range of 243-415 nm and emitted light from blue to yellow. Their capacity for light emission under voltage was preliminarily tested in devices with an active layer consisting of a neat compound and a blend with PVK:PBD. The diodes emitted green or red light.
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The thermal, mechanical and electrical properties of polymeric composites combined using polythiophene (PT) dopped by FeCl3 and polyamide 6 (PA), in the aspect of conductive constructive elements for organic solar cells, depend on the molecular structure and morphology of materials as well as the method of preparing the species. This study was focused on disclosing the impact of the polythiophene content on properties of electrospun fibers. The elements for investigation were prepared using electrospinning applying two substrates. The study revealed the impact of the substrate on the conductive properties of composites. In this study composites exhibited good thermal stability, with T5 values in the range of 230-268 °C that increased with increasing PT content. The prepared composites exhibited comparable PA Tg values, which indicates their suitability for processing. Instrumental analysis of polymers and composites was carried out using Fourier Transform Infrared spectroscopy (FT-IR), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), dynamic mechanical thermal analysis (DMTA) and scanning electron microscopy (SEM).
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The effect of TiO2 nanostructures such as nanoparticles, nanowires, nanotubes on photoanode properties, and dye-sensitized solar cells photovoltaic parameters were studied. The series of dye-sensitized solar cells based on two dyes, that is, commercially N719 and synthesized 3,7'-bis(2-cyano-1-acrylic acid)-10-ethyl-phenothiazine were tested. Additionally, the devices containing a mixture of this sensitizer and chenodeoxycholic acid as co-adsorbent were fabricated. The amount of adsorbed dye molecules to TiO2 was evaluated. The prepared photoanodes with different TiO2 nanostructures were investigated using UV-Vis spectroscopy, optical, atomic force, and scanning electron microscopes. Photovoltaic response of constructed devices was examined based on current-voltage characteristics and electrochemical impedance spectroscopy measurements. It was found that the highest UV-Vis absorption exhibited the photoanode with nanotubes addition. This indicates the highest number of sensitizer molecules anchored to the titanium dioxide photoanode, which was subsequently confirmed by dye-loading tests. The highest power conversion efficiency was (6.97%) for solar cell containing nanotubes and a mixture of the dyes with a co-adsorbent.
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Elastic constructive elements prepared by electrospinning using polyacrylonitrile/polyaniline (PAN/PANI) electroconductive composites were prepared and investigated in terms of their thermal and mechanical properties. This study was focused on the impact of the type of counterion of polyaniline and the PANI content in composites on the thermal, conductive and morphological properties of electrospun fibers. In this study, composites obtained from PANI doped with sulfuric acid showed the highest conductivity, and composites obtained from PANI doped with hydrochloric acid showed the highest thermal stability. All obtained composites exhibited good thermal stability, with T5 values in the range of 230-268 °C that increased with increasing PANI content. The prepared composites exhibited comparable PAN Tg values, which indicates their suitability for processing. Instrumental analysis of polymers and composites was carried out using UV-visible spectroscopy, thermogravimetric analysis, differential scanning calorimetry, dynamic mechanical thermal analysis and scanning electron microscopy.
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The ground- and excited-state properties of three novel complexes [ReCl(CO)3(Ln-κ2N)] bearing 2,2':6',2''-terpyridine, 2,6-di(thiazol-2-yl)pyridine and 2,6-di(pyrazin-2-yl)pyridine functionalized with 9-carbazole attached to the central pyridine ring of the triimine core via phenylene linkage were investigated by spectroscopic and electrochemical methods and were simulated using density functional theory (DFT) and time-dependent DFT. To get a deeper and broader understanding of structure-property relationships, the designed Re(i) carbonyl complexes were compared with previously reported analogous systems - without any groups attached to the phenyl ring and bearing pyrrolidine instead of 9-carbazole. The results indicated that attachment of the N-carbazolyl substituent to the triimine core has less influence on the nature of the triplet excited state of [ReCl(CO)3(Ln-κ2N)] than the pyrrolidine group. Additionally, the impact of the ligand structural modifications on the light emission of the Re(i) complexes under external voltage was preliminarily examined with electroluminescence spectra of diodes containing the synthesized new molecules in an active layer.