Donor Substituents Research Articles

Highly Efficient Blue Thermally Activated Delayed Fluorescence Emitters with a Triphenylamine‐Based Macrocyclic Donor

AbstractThis work reports the incorporation of a triphenylamine‐based macrocyclic donor to design new donor‐π‐acceptor‐configured blue thermally activated delayed fluorescence (TADF) emitters. The X‐ray structure analyses manifest the degree of twisted conformations that can be modulated by methyl substituents of the π‐bridge and macrocyclic donor, leading to well‐separated highest occupied natural transition orbital and lowest unoccupied natural transition orbital frontier orbitals, thus sufficiently small singlet–triplet energy difference (ΔEST) for TADF. The theoretical analyses elucidate the structure–property relationship and reveal the beneficial effect of macrocyclic donor on increasing reverse intersystem crossing (RISC) process that can contribute to improved triplet‐upconversion efficiency. The blue device employing c‐NN‐TRZ as emitter gave a maximum external quantum efficiecny (EQEmax) of 26.3% as compared to that (19.1%) of the device using the model compound DPA‐MeTRZ without the macrocyclic donor, suggesting the contribution of macrocyclic donor to enhance device performance. Benefiting from the combined advantages of macrocyclic donor and methyl substituents, the device incorporating c‐NN‐MeTRZ as emitter achieves an outstanding EQEmax of 32.2%, which is attributed to the more horizontally oriented emission dipoles as well as the significantly accelerated RISC rate constant (kRISC) resulting from reduced ΔEST. This work represents a new strategy of designing twisted TADF emitter incorporating macrocyclic donor to achieve highly efficient blue device.

Towards Efficient and Stable Donor-Acceptor Luminescent Radicals.

In contrast to closed-shell luminescent molecules, the electronic ground state and lowest excited state in organic luminescent radicals are both spin doublet, which results in spin-allowed radiative transitions. Most reported luminescent radicals with high photoluminescent quantum efficiency (PLQE) have a donor-acceptor (D-A•) chemical structure where an electron-donating group is covalently attached to an electron-withdrawing radical core (A•). Understanding the main factors that define the efficiency and stability of D-A• type luminescent radicals remains challenging. Here, wedesigned and synthesized a series of tri(2,4,6-trichlorophenyl)methyl (TTM) radical derivatives with donor substituents varying by their extent of conjugation and their number of imine-type nitrogen atoms. The experimental results suggest that the luminescence efficiency and stability of the radicals are proportional to the degree of conjugation but inversely proportional to the number of imine nitrogen atoms in the substituents. These experimental trends are very well reproduced by density functional theory calculations. The theoretical results indicate that both the luminescence efficiency and radical stability are related to the energy difference between the charge transfer (CT) and local-excitation (LE) states, which decreases as either the number of imine nitrogen atoms in the substituent increases or its conjugation length decreases.

Deep eutectic solvents as reusable catalysts and promoter for the greener syntheses of small molecules: Recent advances

Deep eutectic solvents (DESs) are significant environmentally benign media in the field of green chemistry. They are known not only for their inexpensive nature, biodegradability, non-toxicity, and bioavailability, but also for recyclability and their ease of preparation and purification. DESs are made up of hydrogen bond donor substituents (such as urea, carboxylic acid, glycerol, metals, etc.) and hydrogen bond acceptor substituents such as halide salts; they have a lower melting point than each substituent comprising the mixture. DESs find applications in biotransformation, gas separation, biomass valorization, electrochemistry, extraction, and dissolution process as well as in material chemistry and other assorted fields of chemistry. Interestingly, DESs fulfil a unique dual role as green solvents, promoters and catalysts in organic syntheses. Thus, it is noteworthy that chemical progresses and transformation with external catalysts in cross-coupling reactions, oxidations and reductions are not covered in this overview. This review mostly focuses on leading-edge applications of DES as a reusable catalyst in the expeditious synthesis of assorted small molecules central in the assembly of broad-spectrum pharmaceuticals, and total synthesis of common natural products.

Imaging of lipid droplets using coumarin fluorophores in live cells and C. elegans.

Fluorescent probes offer incredibly effective tools for visualizing the dynamic morphology of lipid droplets (LDs) and investigating their physiological interactions. In this work, we have utilized solvatochromic coumarin probes bearing nitrile and ester substituents for live-cell imaging. The fluorescence probes are characterized by a donor (diethylamino) and acceptor (nitrile and/or ester) substituents and a rotatable double bond. The designed architecture allows investigation of environmental sensitivity apart from providing excellent ability to target sub-cellular organelles. The synthesized fluorophores showed low cytotoxicity and excellent localization within the lipid droplets. Further, the fluorophores were also utilized to study viscosity changes within the LDs induced by Nystatin. More importantly, we also demonstrate imaging of LDs in multi-cellular animal models such as C. elegans.

Carbodicarbenes and Striking Redox Transitions of their Conjugate Acids: Influence of NHC versus CAAC as Donor Substituents.

Herein, a new type of carbodicarbene (CDC) comprising two different classes of carbenes is reported; NHC and CAAC as donor substituents and compare the molecular structure and coordination to Au(I)Cl to those of NHC-only and CAAC-only analogues. The conjugate acids of these three CDCs exhibit notable redox properties. Their reactions with [NO][SbF6 ] were investigated. The reduction of the conjugate acid of CAAC-only based CDC with KC8 results in the formation of hydrogen abstracted/eliminated products, which proceed through a neutral radical intermediate, detected by EPR spectroscopy. In contrast, the reduction of conjugate acids of NHC-only and NHC/CAAC based CDCs led to intermolecular reductive (reversible) carbon-carbon sigma bond formation. The resulting relatively elongated carbon-carbon sigma bonds were found to be readily oxidized. They were, thus, demonstrated to be potent reducing agents, underlining their potential utility as organic electron donors and n-dopants in organic semiconductor molecules.

Facile synthesis of spiro-core-based hole-transporting material for high-performance and stable perovskite solar cells

Two new spirocore-based hole-transporting materials (HTMs), spiro-1 and spiro-2, with 5H-spiro(benzo[1,2-b:6,5-b']dithiophene-4,4′-cyclopenta[2,1-b:3,4-b′]dithiophen)-5-one moiety connected with multiple triphenylamine donor substituents are synthesized via two-step synthesis with low cost and simple procedures and used as HTM in perovskite solar cells (PSCs). The correlation between different HTM structures and the performance of the PSCs was investigated systematically. Experiments results on the thermal stability, photophysical, electrochemical, charge-transporting, as well as film-forming properties show that spiro-1 and spiro-2 are suitable candidate as HTMs for PSCs. The fabricated PSCs with spiro-1 and spiro-2 as HTMs achieved an excellent power conversion efficiency (PCE) of 21.67 % and 19.65 % respectively, both with negligible hysteresis. The obtained PCE of 21.67 % based on spiro-1 is higher than that of the reference solar cell using traditional HTM of spiroOMeTAD (20.59 %) under the same conditions. It may be ascribed to the higher hole mobility, the more efficient hole extraction at the HTM/perovskite interface, the better film morphology. Moreover, the devices based on the new HTM showed good long-term stability and maintained over 80 % of their initial efficiency under continuous stressing at 85 °C and light illumination at 50 °C for 500 h in air without any encapsulation, which were superior to that of spiroOMeTAD. This work demonstrates that the newly developed spirofused molecules are promising HTMs for highly efficient and stable PSCs for the future commercialization of PSCs.

Ultrafast photoinduced dynamics of a donor-(mathrm pi)bridge-acceptor based merocyanine dye

Merocyanine dyes are of great interest amongst researchers due to their nonlinear optical (NLO) properties and solvatochromism. Molecular structure of these dyes constitutes conjugated pathway between the donor and acceptor substituents, with lowest energy transition of mathrm pi–mathrm pi* character. To rationalize the design of these dyes and deduce structure-property relationship, it is eminent to unravel the excited state dynamics in these complex molecular structures in different solvents. Here we have studied excited state dynamics of a merocyanine dye known as HB194, which has shown commendable efficiency in small molecule based bulk heterojuction solar cells. We have employed femtosecond transient absorption in combination with the quantum chemistry calculations to unravel the solvent dependent charge transfer dynamics of HB194. The excited state decays of the HB194 in different solvents show multi-exponential components. The analysis of the time-resolved data reveals that the polar solvents induce conformationally relaxed intramolecular charge transfer state. In non-polar solvent cyclohexane, only solvent-stabilized ICT state is observed. Additionally, we observe an anomalously red-shifted emission in ethylene glycol centred at sim 750 nm. Our computational calculations suggest the presence of molecular dimers resulting into observed red-shifted emission band. Our work therefore underscores the importance of gathering molecular-level insight into the system-bath interactions for designing next generation merocynanine-based solvatochromic dyes.

Toward efficient functionalization of polystyrene backbone through ketene chemistry: Synthesis, characterization, and DFT study

AbstractIn this study, polystyrene was functionalized with Meldrum's acid toward the introduction of the ketenes (CCO) system to its backbone for producing a dramatically reactive intermediate. Meldrum's acid, as a ketene source, was reacted by poly(styrene‐co‐p‐chloromethyl styrene) through a simple nucleophilic reaction to synthesize poly(styrene‐co‐styryl Meldrum's acid). Then, the pendant Meldrum's acid under thermal treatment converted to ketene intermediate resulting in highly reactive polystyrenes derivatives, which rapidly reacted by nucleophilic reagents to afford ultimate organic building blocks. The polystyrene derivatives were characterized using elemental analysis, FT‐IR, high‐resolution solid‐state NMR, thermogravimetric analysis (TGA), and differential thermogravimetric analysis (DTG). To clarify the evolutionary mechanisms of polystyrene products, density functional theory (DFT) method B3LYP with the 6–311++G(2d,p) basis set was used. We studied the preparation of polystyrene model compounds through Meldrum's acid thermolysis and nucleophilic substitution. The kinetic and thermodynamic parameters in all reactions and the structural and electronic properties of all molecules were calculated. These data exhibited that based on Gibbs Free energy values, the structure of syndiotactic polystyrene is more stable than that of isotactic polystyrene. Furthermore, it was found that the presence of an electron donor or acceptor substituent on the polystyrene structure affects the electronic bandgap.

Effects of Lewis Basicity and Acidity on σ-Hole Interactions in Carbon-Bearing Complexes: A Comparative Ab Initio Study.

The effects of Lewis basicity and acidity on σ-hole interactions were investigated using two sets of carbon-containing complexes. In Set I, the effect of Lewis basicity was studied by substituting the X3/X atom(s) of the NC-C6H2-X3 and NCX Lewis bases (LB) with F, Cl, Br, or I. In Set II, the W-C-F3 and F-C-X3 (where X and W = F, Cl, Br, and I) molecules were utilized as Lewis acid (LA) centers. Concerning the Lewis basicity effect, higher negative interaction energies (Eint) were observed for the F-C-F3∙∙∙NC-C6H2-X3 complexes compared with the F-C-F3∙∙∙NCX analogs. Moreover, significant Eint was recorded for Set I complexes, along with decreasing the electron-withdrawing power of the X3/X atom(s). Among Set I complexes, the highest negative Eint was ascribed to the F-C-F3∙∙∙NC-C6H2-I3 complex with a value of -1.23 kcal/mol. For Set II complexes, Eint values of F-C-X3 bearing complexes were noted within the -1.05 to -2.08 kcal/mol scope, while they ranged from -0.82 to -1.20 kcal/mol for the W-C-F3 analogs. However, Vs,max quantities exhibited higher values in the case of W-C-F3 molecules compared with F-C-X3; preferable negative Eint were ascribed to the F-C-X3 bearing complexes. These findings were delineated as a consequence of the promoted contributions of the X3 substituents. Dispersion forces (Edisp) were identified as the dominant forces for these interactions. The obtained results provide a foundation for fields such as crystal engineering and supramolecular chemistry studies that focus on understanding the characteristics of carbon-bearing complexes.

Spectroscopic Studies of Styrylquinoline Copolymers with Different Substituents.

The aim of the study was to present the influence of various styrylquinoline (StQ) substituents on the luminescence, structural, and optical properties of StQ-containing copolymers. StQ-containing copolymers were synthesized by free-radical thermoinitiated polymerization. The calculations of the copolymerization ratios for the obtained copolymers were based on the basis of the integrated peak areas of the 1H NMR spectra in CDCl3. The luminescence measurements show that the change in the nature of the electron-donating and electron-withdrawing of the substituent shifts the emission band to longer wavelengths and causes a transition from blue fluorescence to green or yellow and orange (or even white), regardless of the electronic nature of the introduced substituent group. The structural properties were measured by Fourier-Transform Infrared (FTIR) and Raman spectroscopies. For all of the compounds, we observed similarities in the bands in FTIR and Raman measurements. The optical parameters were obtained from the absorbance measurements. Additionally, Scanning Electron Microscopy (SEM) was used to study the surface topography of the thin layers on the glass substrate. The SEM images confirm that we obtained smoother layers for two copolymers. The computational Density Functional Theory (DFT) analysis fully supports the beneficial features of the analyzed systems for their applications in optoelectronic devices. Based on the obtained results, it can be concluded that all of the studied styrylquinolines are promising materials for applications in organic light-emitting diodes (OLEDs). However, COP1 with an OCH3 donor substituent possess a wider luminescence band, and its layer is smoother and more transparent.

Design, Regioselective Synthesis, and Photophysical Properties of Perfluoronaphthalene-Based Donor-Acceptor-Donor Fluorescent Dyes.

A one-step route to a series of perfluoronaphthalene-based donor (D)-acceptor (A)-D fluorescent dyes with various electron-donating groups was developed. The perfluoronaphthalene moiety in the D-A-D dyes served as a good electron-accepting aromatic ring with excellent intramolecular charge transfer properties, as determined by density functional theory calculations and measurements of the fluorescence properties in solution, in poly(methyl methacrylate) (PMMA) films, and in crystal form. Notably, replacing the naphthalene ring with perfluoronaphthalene in the D-A-D dyes carrying the phenothiazine moiety not only stabilized the highest occupied molecular orbital and lowest unoccupied molecular orbital energy levels but also reduced the energy band gap to change the emission color from blue to yellow. Among the four synthesized perfluoronaphthalene D-A-D dyes, those bearing diphenylamino groups afforded the best fluorescence quantum yields in Et2O solution (0.60) and in PMMA film (0.65) because the propeller structure of the diphenylamino group that acts as a donor substituent effectively suppresses radiation-free deactivation. In contrast, in the crystalline state, the carbazoyl-bearing D-A-D dye provided the best fluorescence quantum yield (0.35) because the radiation-free inactivation was suppressed by π-πF stacking at the donor site, which was confirmed by single-crystal X-ray analysis.

Bay‐Monosubstitution with Electron‐Donating Group as an Efficiently Strategy to Functionalize Perylene Imide Polymer for Enhancing Photocatalytic Oxygen Evolution Activity

AbstractIt is still a challenge to develop an organic conjugated photocatalyst with a high O2 evolution rate. Functionalization organic polymer photocatalysts is an effective way to enhance photocatalytic performance. In this study, a series of perylene imide polymers (PDIs) are prepared by introducing different number of phenyl groups at bay position of PDI, and the influence of the number of substituents on charge separation and photocatalytic activity is investigated. It reveals that monosubstituted PDI exhibits the highest O2 evolution rate of 2524.88 µmol g–1 h–1 under visible light illumination without any cocatalyst. The excellent performance ascribes to the push–pull intramolecular charge transfer and the high crystallinity, which significantly promote separation and transfer of photoinduced charge. However, the O2 evolution rate dramatically drops with the number of substituent groups increase because introducing more groups at the bay position of PDI decreased charge local excitation of the PDI core and occupied the O2 evolution active site. In addition, it is found that increasing the number of electron–donor substituent groups would seriously destroy the crystallinity, leading to a decrease in the O2 evolution rate. This study highlights a reasonably structural modification strategy to enhance the O2 evolution rate of the PDI polymer by electron‐donating group monosubstitution.

The catalytic activity difference of bis(phosphinite) pincer ligated Pt(II) thiolate and hydride complexes against hydrosilylation of aldimines

• POCOP pincer Pt thiolate and hydride complexes are good catalysts for hydrosilylation of aldimines • The thiolate complexes are more active than the hydride complexes • The reactions feature with good functional group compatibility and wide substrate scope • The expected amine products can be isolated in good to excellent yields In order to get information about the catalytic activities of bis(phosphinite) (POCOP) pincer ligated group 10 metal thiolate and hydride complexes against the hydrosilylation of unsaturated carbon-heteroatom bonds, platinum(II) complexes [2,6-( t Bu 2 PO) 2 C 6 H 3 ]PtX (X = SH, 1a; SPh, 1b; H, 1c) and [2,6-( i Pr 2 PO) 2 C 6 H 3 ]PtH (2) were applied to the catalytic hydrosilylation of aldimines. It was found that both auxiliary ligand and donor substituent play very important roles in affecting the catalytic activity of the platinum center. The hydride complex 1c is almost inactive in catalyzing the reactions; however, the hydride complex 2, which processes less bulky donor substituents ( i Pr vs t Bu), is an active catalyst. Meanwhile, the thiolate complexes 1a and 1b, which have the same donor substituents as 1c, are active catalysts and 1a is among most effective catalysts for this type of reaction. The catalytic reactions are featured with a wide substrate scope with relatively high turnover frequencies. Both aromatic and aliphatic aldimines were successfully hydrosilylated and the expected amines were isolated in good to excellent yields after basic hydrolysis of the hydrosilylation products. Functional groups such as OMe, halogens and internal C=C double bond were unaffected during the reactions. Although the hydride complex 2 is an active catalyst, it is less effective than the thiolate complex 1a despite the fact that the metal center in 2 is less sterically hindered by the donor substituents. As a result, the thiolate complexes are more active than the hydride complexes in catalyzing the reactions. The possible reasons for the different catalytic activities of these complexes are discussed.

In Silico Screening of Two‐Photon Absorption Properties of a Large Set of Bis‐Difluoroborate Dyes

AbstractIn this work we strive to unravel the relationships between the two‐photon absorption (2PA) cross‐sections and structural modifications in an extended panel (280 compounds) of large difluoroborate dyes. More specifically, we use theoretical tools based on Time‐Dependent Density Functional Theory (TD‐DFT), to predict the one and two‐photon absorption properties of all compounds. The BF2‐carrying dyes usually posses a great interest for 2PA bioapplications as smartly designed BF2‐derivatives show good photophysical properties and high quantum yields in aqueous medium. For practical applications, it is important to maximize their 2PA response as well as absorption wavelength. This is why we explore here various strategies for maximizing the 2PA cross‐section: core modifications, multi‐branching, variation of the nature and length of the π‐conjugated linkers, addition of various donor and acceptor substituents. Our results suggest that large values of 2PA cross‐section and redshifted absorption wavelength can be achieved for all studied cores by using the vinylene‐type linkers and asymmetrical substitution with at least one strong peripheral donor group.

A combined QTAIM/IRI topological analysis of the effect of axial/equatorial positions of NH2 and CN substituents in the [(PY5Me2)MoO]+ complex

By means of the Interaction Region Indicator (IRI) and Quantum Theory of Atoms in Molecules (QTAIM), the influence exerted by NH2 (amino) and CN (cyano) as electron donor and electron acceptor substituent groups, respectively, located at para–positions of axial and equatorial pyridine rings of derivatized complexes coming from the [(PY5Me2)MoO]+ complex during the hydrogen molecular release in the gas phase was analyzed. In any case, a H–H covalent bond is forming at the transition state, with a strengthening of the electron density of 5.5% when the substituent group involved is NH2 at the para–position of the axial pyridine ring. However, there was no difference between NH2 and CN when these substituent groups are located at the para–positions of the equatorial pyridine rings. The topological properties of electron densities from the QTAIM are not perturbed by the electron donor and electron acceptor nature of the substituents, even when these substituent groups are located at the axial or equatorial pyridine rings of the Mo–based complex.

Spectral and generation properties of new coumarins – benzopyrylium derivatives

The spectral and generation parameters of coumarins, benzopyrylium derivatives, in ethanol and acetonitrile under coherent excitation were studied. It was found that the absorption spectra of the investigated compounds contain several maxima and the structuredness of the spectra is associated with their bichromophoric structure. It is shown that these organic dyes are bichromophoric compounds. It is noted that the nature of the substituents in positions 6 and 7 of the coumarin base and positions 6′ and 7′ of the benzopyrylium core determines their spectral-luminescent and lasing properties. It is demonstrated that the presence of substituents in certain positions of the coumarin base and the benzopyrylium core changes the conformation of the molecule and, accordingly, the dipole moments and oscillator strengths of the transition. The generation ability of coumarins of this class manifests itself only in the presence of the strongest donor substituents (for example, Et2N and OH) in position 7, and sufficiently strong acceptors in positions 6′ and 7′. Lasing was obtained in the spectral region of 730 –740 nm on dyes – benzopyrylium derivatives.

Cyclic voltammogram analysis of the 3,3´- (1,4-phenylene) perchlorates

As a consequence of a three-stage synthesis from terephthalic aldehyde, a series of 3,3 '- (1,4-phenylene) perchlorates including methyl, hydrogen, acetyl, bromio, methoxy and nitro groups (R = Br, H, Me). The matching formazans were reacted with formalin in dioxane in the presence of perchloric acid to produce tetrazin ium salts. Formazans were synthesized by reacting terephthalic aldehyde phenylhydrazone with ar ene diazonium tosylates in a DMF/pyridine combination. The use of ar ene diazonium tosylates greatly simplified the separation and purification of formazans. The p henylhydrazone was produced in aqueous dioxane using the usual approach from terephthalic aldehyde and phenylhydrazine/hydrochloric acid. Individual f ormazans and tetrazinium perchlorates were isolated and characterized by elemental analysis, IR, NMR, UV spectroscopy. The electrochemical reduction of tetrazinium perchlorates was investigated using cyclic voltammetry (CV). Thus, all salts in the cathode region have two one-electron reduction peaks, which are connected to the sequential production of a radical cation and a biradical. It was discovered that donor substituents (R: OMe, Me) in the aromatic ring at position 1 accelerate tetrazinium cation reduction, whereas acceptor substituents (R: NO2, COMe,) inhibit this process. On this premise, it was proposed that in the presence of donor substituents in the aromatic ring at position 1, the matching bis-verdazyl radicals should be easily generated. As a result, 3,3'- (1,4-phenylene) perchlorates are possible antecedents of symmetric biradical systems based on verdazyl radicals.

Photochemical Synthesis and Electrochemical and Photophysical Properties of 2,7-Diarylbenzo[1,2-d:4,3-d']bis(thiazoles).

This article focuses on the development of practical approaches to the preparation of benzo[1,2-d:4,3-d']bis(thiazoles) using blue light-induced photochemical cyclization of N,N'-(1,4-aryl)dithioamides in the presence of p-chloranil as a mild oxidant. The proposed method allows to obtain benzo[1,2-d:4,3-d']bis(thiazoles) containing donor substituents in the conjugated chain. Photophysical and (spectro)electrochemical properties of 2,6-di([2,2'-bithiophen]-5-yl)benzo[1,2-d:4,3-d']bis(thiazole) and -benzo[1,2-d:4,5-d']bis(thiazole) are studied in detail. The properties of the synthesized compounds suggest their potential applications for organic electronics.

Ultrafast Excited State Dynamics of Forward and Reverse trans-cis Photoisomerization of Red-Light-Absorbing Indigo Derivatives.

Femtosecond time-resolved transient absorption (TRTA) spectroscopy was carried out to investigate the ultrafast excited state dynamics of both trans → cis and trans ← cis photoisomerization of red-light-absorbing indigo derivatives. For N,N'-bis(tert-butyloxycarbonylmethyl)indigo (tBOMI), the excited state lifetime of the trans-form was measured to be 41 ps while that of the cis-form was as short as 730 fs in acetonitrile (Acn). The excited state lifetime of trans-N,N'-dimethylindigo (DMI) in Acn was also measured to be as short as 10 ps. These values are much shorter than those of the blue-light-absorbing trans-forms of indigo derivatives such as N,N'-diacetylindigo (DAI) and thioindigo (ThI). The chromophore of indigo is composed of two pairs of electron donor and acceptor substituents conjugated in the shape of a letter "H" (so-called "H-chromophore"), although DFT and TDDFT calculations suggest that the charge transfer (CT) character is not very significant. Nevertheless, when a weak CT within the H-chromophore is promoted, the absorption band shifts to longer wavelengths and the excited state lifetime shortens. For the photoisomerization of DAI and ThI, a relatively long excited state lifetime is required for the photoisomerization, while for tBOMI and DMI, a vibrationally hot ground state that overcomes the energy barrier in the ground state is produced by rapid nonradiative decay through conical intersection. In the case of cis-tBOMI, the repulsion between the two adjacent negatively charged carbonyl groups and the weakening of the central C═C double bond in the S1 state twist the molecule, shorten the excited state lifetime, and increase the quantum yield of the trans ← cis photoisomerization.

Carbazole-based hole-transport materials for efficient Perovskite solar cells. A computational study

In this study, DFT calculations carried out using Carbazole-based HTMs substituted with dimethoxy phenylamine units (DMPA) in positions 2,3,6,7 and 9 are coupled with the experimental results drawn from the literature. The most important challenge for us is to establish a link between the optoelectronic and structural properties of molecules and their performance as HTMs. In this work, we find that the important structural effect is generated by the pyridinic nucleus. The substituents linked to the nitrogen atom of carbazole do not contribute to HOMO or LUMO in most of the studied HTMs. Hence, apart from the illustrated performances, parameters as the contribution of such substituents to being attached to the perovskite, or to the cohesion of the HTM’s molecules contributing to the perovskite stability all prove decisive. The 2,7 substitution favors more stabilization of LUMOs when compared to 3,6 substitution, which leads to a narrow gap for 2,7 homologous. This makes these 2,7-substituted molecules good candidates as light absorbent in Organic Solar cells. The differences in the solar cell performances using these HTMs is mostly linked to the effect of these groups on their intermolecular interactions on one hand, and on the interfacial contact between HTMs and perovskite on the other hand.