Recent advances on organic blue thermally activated delayed fluorescence (TADF) emitters for organic light-emitting diodes (OLEDs)

• Thanh-Tuân Bui,
• Fabrice Goubard,
• Malika Ibrahim-Ouali,
• Didier Gigmes and
• Frédéric Dumur

Beilstein J. Org. Chem. 2018, 14, 282–308, doi:10.3762/bjoc.14.18

• noticed that the photophysical properties and the geometry of molecules that are suspected to be TADF emitters are often investigated by theoretical calculations prior to synthesis, optimizing the chance to get suitable energy levels and the desired ΔEST. This strategy was notably applied to the design of

• TADF blue emitters containing triarylboron accepting units. Besides, as we will see in this review, the design of a good TADF material by optimizing its structure by theoretical calculations is not sufficient to ensure the fabrication of highly emissive OLEDs. As observed for phosphorescent emitters

• diphenylamine unit of D1 by a tert-butyl-substituted carbazole unit in D3, the 3ππ* state was considerably destabilized, raising its energy level and decreasing ΔEST. Parallel to this, a greater separation of the HOMO and LUMO orbitals was evidenced by theoretical calculations for D3, as a result of a larger

Halogen-containing thiazole orange analogues – new fluorogenic DNA stains

• Aleksey A. Vasilev,
• Meglena I. Kandinska,
• Stanimir S. Stoyanov,
• Stanislava B. Yordanova,
• David Sucunza,
• Juan J. Vaquero,
• Obis D. Castaño,
• Stanislav Baluschev and
• Silvia E. Angelova

Beilstein J. Org. Chem. 2017, 13, 2902–2914, doi:10.3762/bjoc.13.283

• the theoretical calculations. Theoretically calculated absorption maximа for the couples 5a/5c and 5b/5d differ by 8 nm and 11 nm, respectively. The first excited states are determined by HOMO (highest occupied molecular orbital)→LUMO (lowest unoccupied molecular orbital) transitions with oscillator

• ) in methanol for compounds 5a–d, TO and TO-7Cl in methanol. Supporting Information Supporting Information File 486: Characterisation data for the compounds: NMR and GS–MS spectra; validation of the theoretical computations; photostabilities at 532 nm. Acknowledgements The theoretical calculations

2-Methyl-2,4-pentanediol (MPD) boosts as detergent-substitute the performance of ß-barrel hybrid catalyst for phenylacetylene polymerization

• Julia Kinzel,
• Daniel F. Sauer,
• Marco Bocola,
• Marcus Arlt,
• Tayebeh Mirzaei Garakani,
• Andreas Thiel,
• Klaus Beckerle,
• Tino Polen,
• Jun Okuda and
• Ulrich Schwaneberg

Beilstein J. Org. Chem. 2017, 13, 1498–1506, doi:10.3762/bjoc.13.148

• protein FhuA ΔCVFtev. The theoretical calculations are in line with the experimental findings, that FhuA ΔCVFtev is properly folded using refolding buffer with 50 mM MPD, which was confirmed by CD spectroscopy (Figure S1, Supporting Information File 1). 2-Methyl-2,4-pentanediol stabilizes FhuA ΔCVFtev up

Conformational study of L-methionine and L-cysteine derivatives through quantum chemical calculations and ³J_HH coupling constant analyses

• Weslley G. D. P. Silva,
• Carolyne B. Braga and
• Roberto Rittner

Beilstein J. Org. Chem. 2017, 13, 925–937, doi:10.3762/bjoc.13.94

• shown good results for other amino acid derivatives, when comparing theoretical with experimental data [22][23][24]. Although 2 could not be experimentally studied, the theoretical calculations carried out strongly suggest that the conformational equilibrium of 2 and the populations of its conformers

• , experimental NMR spectroscopy measurements and spin-spin coupling constant (3JHH) calculations were performed. The experimental 1H NMR data for 1 (Table 3) indicate that the 3JHaHb1 and 3JHaHb2 coupling constants are almost constant in the studied solvents, supporting our findings through theoretical

• calculations that the conformational equilibria of 1 are not affected by the solvent change. The two different observed values for 3JHaHb1,obs (approximately 5.0 Hz) and 3JHaHb2,obs (approximately 7.0 Hz) confirm that conformers in form b are favored in the equilibrium of 1, since these constants are dependent

Molecular-level architectural design using benzothiadiazole-based polymers for photovoltaic applications

• Vinila N. Viswanathan,
• Arun D. Rao,
• Upendra K. Pandey,
• Arul Varman Kesavan and
• Praveen C. Ramamurthy

Beilstein J. Org. Chem. 2017, 13, 863–873, doi:10.3762/bjoc.13.87

• higher HOMO energy is due to the incorporation of the electron-donating thienothiophene bridge in the polymer backbone. The experimentally obtained values of frontier molecular energy levels follow the same trends with respect to the theoretical calculations. All polymers have deep-lying HOMO energy

• 1.87 eV, respectively. Again, a lower band gap is observed for P3 owing to the extended conjugation over the other polymers. The combined optical, electrochemical, and theoretical calculations are summarized in Table 2. Photoluminescence (PL) quenching studies were performed with pure donor polymers

• . Electrochemical and optical properties along with theoretical calculations. Photovoltaic properties of the devices based on polymers P1, P2 and P3. Supporting Information Supporting Information File 82: Experimental details and characterization data. Acknowledgements The authors gratefully acknowledge the

Regiochemistry of cyclocondensation reactions in the synthesis of polyazaheterocycles

• Patrick T. Campos,
• Leticia V. Rodrigues,
• Andrei L. Belladona,
• Caroline R. Bender,
• Juliana S. Bitencurt,
• Fernanda A. Rosa,
• Davi F. Back,
• Helio G. Bonacorso,
• Nilo Zanatta,
• Clarissa P. Frizzo and
• Marcos A. P. Martins

Beilstein J. Org. Chem. 2017, 13, 257–266, doi:10.3762/bjoc.13.29

• compounds 11a–e were washed with acetonitrile (1 × 1 mL). The reactions done with non-symmetric dinucleophiles 8b, 8e, and 8f furnished isomeric product mixtures. Data obtained from DFT-B3LYP theoretical calculations showed that in the three α-ketoesters 5–7, the carbonyl of the ketone has a larger LUMO

• between β-enaminodiketone and aromatic amidines was highly regioselective. Results obtained from DFT-B3LYP theoretical calculations were in agreement with the experimental data. Using data from HOMO and LUMO coefficients, it was possible to conclude that the reaction is controlled by frontier molecular

• product mixtures were formed when non-symmetric diamines were used as dinucleophiles. Theoretical calculations provided data regarding the stability of these isomeric mixtures. However, the synthesis of imidazolone heterocycles was not achieved. Nevertheless, the N-acylated product was formed from the

Spectral and DFT studies of anion bound organic receptors: Time dependent studies and logic gate applications

• Srikala Pangannaya,
• Neethu Padinchare Purayil,
• Shweta Dabhi,
• Venu Mankad,
• Prafulla K. Jha,
• Satyam Shinde and
• Darshak R. Trivedi

Beilstein J. Org. Chem. 2017, 13, 222–238, doi:10.3762/bjoc.13.25

• upon anion binding (Supporting Information File 1, Table S1). Theoretical calculations afforded absorption maxima at 352 nm and 416 nm for receptor R1 and 361 and 487 nm for R2, respectively. The shift in the absorption maxima for R1–F− and R1–AcO− to 451 and 455 nm and for R2–F− and R2–AcO− to 572 and

Synthesis of spiro[isoindole-1,5’-isoxazolidin]-3(2H)-ones as potential inhibitors of the MDM2-p53 interaction

• Salvatore V. Giofrè,
• Santa Cirmi,
• Raffaella Mancuso,
• Francesco Nicolò,
• Giuseppe Lanza,
• Laura Legnani,
• Agata Campisi,
• Maria A. Chiacchio,
• Michele Navarra,
• Bartolo Gabriele and
• Roberto Romeo

Beilstein J. Org. Chem. 2016, 12, 2793–2807, doi:10.3762/bjoc.12.278

• failed, leading to the degradation of the nitrone and the isolation of the unaltered dipolarophile, so clearly indicating that the steric factors play a crucial role in the cycloaddition process (see computational data). Theoretical calculations The obtained results and stereochemical outcome of the 1,3

Selective and eco-friendly procedures for the synthesis of benzimidazole derivatives. The role of the Er(OTf)₃ catalyst in the reaction selectivity

• Natividad Herrera Cano,
• Jorge G. Uranga,
• Mónica Nardi,
• Antonio Procopio,
• Daniel A. Wunderlin and
• Ana N. Santiago

Beilstein J. Org. Chem. 2016, 12, 2410–2419, doi:10.3762/bjoc.12.235

• , which is frequently associated with these reactions. Theoretical calculations helped to understand the different reactivity established for these reactions. Thus, we found that the charge density on the oxygen of the carbonyl group has a significant impact on the reaction pathway. For instance, electron

• , differences in reactivity were investigated by by means of theoretical calculations. Results and Discussion The benzimidazole core was obtained by air oxidative cyclocondensation of o-phenylenediamine with benzaldehyde under different conditions. In water and in the presence of Er(OTf)3, the diamine and

• -deficient aldehydes under the same conditions. To shed light on this observation, we decided to carry out theoretical calculations, using the BPW91 functional at 6-31+G* level, as implemented in Gaussian 09 [43]. In order to evaluate the effect of the substituent on the reactivity of aldehydes, we used a

Methylenelactide: vinyl polymerization and spatial reactivity effects

• Judita Britner and
• Helmut Ritter

Beilstein J. Org. Chem. 2016, 12, 2378–2389, doi:10.3762/bjoc.12.232

• also shows additional postulated radical reactions including the formation of a bicyclic lactide radical to initiate the main polymerization. Since the spontaneous homolytically C–H cleavage may represent the first step in the reaction cascade, theoretical calculations on a DFT level were conducted

• polymers were obtained, the C–H bonds in the linear MLA-polymer units must be more stable than in the monomeric MLA. Otherwise, crosslinking should take place via spontaneous C–H cleavage and chain recombination. This important point could be verified by IR spectroscopy and also by theoretical calculations

• pull-type α-methylene-δ-valerolactone (MVL). A deviation from classical free-radical polymerization kinetics was found and correlated with significant self-initiation. A mechanism for the radical formation was proposed and supported by theoretical calculations. With the help of a strongly colored 1,1

Determination of the absolute stereostructure of a cyclic azobenzene from the crystal structure of the precursor containing a heavy element

• Reji Thomas and
• Nobuyuki Tamaoki

Beilstein J. Org. Chem. 2016, 12, 2211–2215, doi:10.3762/bjoc.12.212

• enantiomer formed by the reductive debromination. In the previous study with the combination of density functional theoretical calculations (DFT) and electronic circular dichroism (ECD), we have assigned the first and second eluted enantiomers of (E)-2 as R-(−)-(E)-2 and S-(+)-(E)-2, respectively, on a

• with structural data of S-(−)-(E)-1 the absolute stereostructure of its reduced product is determined as R-(−)-(E)-2. The experimentally derived stereostructure completely matches with the absolute structure previously predicted from theoretical calculations. In summary, we demonstrated the

Synthesis and properties of fluorescent 4′-azulenyl-functionalized 2,2′:6′,2″-terpyridines

• Adrian E. Ion,
• Liliana Cristian,
• Mariana Voicescu,
• Masroor Bangesh,
• Augustin M. Madalan,
• Daniela Bala,
• Constantin Mihailciuc and
• Simona Nica

Beilstein J. Org. Chem. 2016, 12, 1812–1825, doi:10.3762/bjoc.12.171

• can influence the emission behavior and it may be changed from dominant S2→S0 fluorescence to either dual fluorescence or to dominant S1→S0 fluorescence. Theoretical calculations Methods The geometries of 4a and 4b with initial atomic coordinates taken from X-ray crystal structure were optimized with

Cp₂TiCl/D₂O/Mn, a formidable reagent for the deuteration of organic compounds

• Antonio Rosales and
• Ignacio Rodríguez-García

Beilstein J. Org. Chem. 2016, 12, 1585–1589, doi:10.3762/bjoc.12.154

• -ordination of water to Cp2TiCl might weakens the strength of the O–H bond. In this way a single electron transfer from titanium to oxygen might facilitate the HAT from the titanocene aqua-complex to the free radicals. Theoretical calculations supported that the coordination of water to Cp2TiIIICl weakens the

• cyclic voltammetry, theoretical calculations and electro-paramagnetic resonance techniques studies [28][34]. These results are in agreement with the previously reported results by Wood et al. [35] and Renaud et al. [36] describing the effect of complexation with a Lewis acid on the strength of the O–H

Is conformation a fundamental descriptor in QSAR? A case for halogenated anesthetics

• Maria C. Guimarães,
• Mariene H. Duarte,
• Josué M. Silla and
• Matheus P. Freitas

Beilstein J. Org. Chem. 2016, 12, 760–768, doi:10.3762/bjoc.12.76

• suggesting that these 2D MD´s can be advantageous over some three-dimensional descriptors. Keywords: conformational analysis; isoflurane; QSAR; theoretical calculations; volatile anesthetics; Introduction Quantitative structure–activity relationship (QSAR) studies try to find a correlation between chemical

cis–trans-Amide isomerism of the 3,4-dehydroproline residue, the ‘unpuckered’ proline

• Vladimir Kubyshkin and
• Nediljko Budisa

Beilstein J. Org. Chem. 2016, 12, 589–593, doi:10.3762/bjoc.12.57

• analogues which possess a 3,4-double bond: 3,4-dehydroproline and 4-trifluoromethyl-3,4-dehydroproline. Both indicate a flat pyrroline ring in their crystal structures, in agreement with previous theoretical calculations. In solution, the peptide mimics exhibit an almost unchanged equilibrium of the trans

Mechanism, kinetics and selectivity of selenocyclization of 5-alkenylhydantoins: an experimental and computational study

• Biljana M. Šmit,
• Radoslav Z. Pavlović,
• Dejan A. Milenković and
• Zoran S. Marković

Beilstein J. Org. Chem. 2015, 11, 1865–1875, doi:10.3762/bjoc.11.200

• theory (DFT) methods. The pathways of the reaction are investigated in detail. There are two regioselective pathways related to 5-exo and 6-endo products. Theoretical calculations and the monitoring of the cyclization reaction using 1H NMR spectroscopy are in a good agreement with the proposed mechanism

• sustains the statement about existing of such an intermediate. Theoretical calculations of the 1H chemical shifts for intermediate (S,R/S,S)-INT1 are in agreement with the observed values (Table 1, Figure 1). Starting 5-alkenylhydantoin 1 was synthesized from 6-methyl-hepten-2-on [24] by Bucherer–Bergs

• regio- and stereoisomerism of all intermediates and products were done on the basis of excellent correlation of experimental and calculated 1H chemical shifts as well as relative free energies. Theoretical calculations are in good agreement with our experimental results. Experimental All commercials

Tetrathiafulvalene-based azine ligands for anion and metal cation coordination

• Awatef Ayadi,
• Aziz El Alamy,
• Olivier Alévêque,
• Magali Allain,
• Nabil Zouari,
• Mohammed Bouachrine and
• Abdelkrim El-Ghayoury

Beilstein J. Org. Chem. 2015, 11, 1379–1391, doi:10.3762/bjoc.11.149

• that occurs in ligand L2 leading to a resonance structure that involves the C=N hydrazone bond as it can be seen in (Figure S2, Supporting Information File 1). Theoretical calculations Theoretical calculations based on density functional theory (DFT) methods have been performed with the Gaussian 09

Surprisingly facile CO₂ insertion into cobalt alkoxide bonds: A theoretical investigation

• Willem K. Offermans,
• Claudia Bizzarri,
• Walter Leitner and
• Thomas E. Müller

Beilstein J. Org. Chem. 2015, 11, 1340–1351, doi:10.3762/bjoc.11.144

• of zinc succinate. This was used to explain the activity of the former three and the inactivity of the latter. Theoretical calculations revealed a decrease in the activation barrier for the homopolymerisation as well as the copolymerisation step with increasing metal–metal distance. Moreover, the

Thiazole-induced rigidification in substituted dithieno-tetrathiafulvalene: the effect of planarisation on charge transport properties

• Rupert G. D. Taylor,
• Joseph Cameron,
• Iain A. Wright,
• Neil Thomson,
• Olena Avramchenko,
• Alexander L. Kanibolotsky,
• Anto R. Inigo,
• Tell Tuttle and
• Peter J. Skabara

Beilstein J. Org. Chem. 2015, 11, 1148–1154, doi:10.3762/bjoc.11.129

• charge transfer (CT) from the TTF to the electron-deficient thiazole units, facilitated due to their planarity. The structural properties of each compound will be expanded upon in the theoretical calculations section. Solution-state cyclic voltammetry was employed to determine the highest occupied

• , resulting in donation from the nitrogen lone pair to the sulfur atoms of the TTF unit increasing the electron density on the TTF unit and destabilising the HOMO. Theoretical calculations DFT calculations were carried out using the CAM-B3LYP [17] functional and TZVP [18] basis set in dichloromethane with the

New tris- and pentakis-fused donors containing extended tetrathiafulvalenes: New positive electrode materials for rechargeable batteries

• Shintaro Iwamoto,
• Yuu Inatomi,
• Daisuke Ogi,
• Satoshi Shibayama,
• Yukiko Murakami,
• Minami Kato,
• Kazuyuki Takahashi,
• Kazuyoshi Tanaka,
• Nobuhiko Hojo and
• Yohji Misaki

Beilstein J. Org. Chem. 2015, 11, 1136–1147, doi:10.3762/bjoc.11.128

• obtained as stable solids. Theoretical calculations We performed theoretical calculations of 5A, 6Aa and 7Aa by using the Gaussian 09 program based on the density functional theory (DFT) at the B3LYP/6-31G(d) level [27]. Their HOMO and HOMO–n (n = 1–2 and 1–4) of the trans isomers of 5a, 6a and 8a are

Single-molecule conductance of a chemically modified, π-extended tetrathiafulvalene and its charge-transfer complex with F₄TCNQ

• Raúl García,
• M. Ángeles Herranz,
• Edmund Leary,
• M. Teresa González,
• Gabino Rubio Bollinger,
• Marius Bürkle,
• Linda A. Zotti,
• Yoshihiro Asai,
• Fabian Pauly,
• Juan Carlos Cuevas,
• Nicolás Agraït and
• Nazario Martín

Beilstein J. Org. Chem. 2015, 11, 1068–1078, doi:10.3762/bjoc.11.120

• theoretical calculations. To the best of our knowledge, these are the first reported single-molecule conductance measurements on a molecular charge-transfer species. Keywords: break junction measurements; charge-transfer complex; DFT-based transport; molecular electronics; tetrathiafulvalene; Introduction

• experimental resolution, based on the value we measure for the CT complex. Ab initio calculations To gain insight into the conduction mechanism of compound 5, we performed theoretical calculations based on a combination of density functional theory (DFT) and Green’s functions techniques within the framework of

• functionalized with two (p-acetylthio)phenylethynyl substituents at positions 2 and 6 of the anthracene central core. We then describe single-molecule conductance measurements on this new derivative, along with measurements of the charge-transfer complex formed with F4TCNQ. Finally, we present theoretical

Glycoluril–tetrathiafulvalene molecular clips: on the influence of electronic and spatial properties for binding neutral accepting guests

• Yoann Cotelle,
• Marie Hardouin-Lerouge,
• Stéphanie Legoupy,
• Olivier Alévêque,
• Eric Levillain and
• Piétrick Hudhomme

Beilstein J. Org. Chem. 2015, 11, 1023–1036, doi:10.3762/bjoc.11.115

• central double bond of each TTF moiety, the intramolecular wall-to-wall distance was determined to be equal to 8.25 Å and 7.41 Å for clip 2 and 3, respectively (Figure 2) [18]. Then the corresponding wall-to-wall distance between the two TTF units was determined by theoretical calculations using the semi

• . Structures of molecular clips 1–4. Intramolecular distances between TTF moieties from X-ray analysis for clips 2 and 3 and theoretical calculations for clip 4. Cyclic voltammograms of molecular clips 1, 2, 3, 4 and F4-TCNQ at 10−3 M in 0.1 M TBAPF6/CH2Cl2/CH3CN 3:1 on a glassy carbon electrode at 100 mV·s−1

Trifluoromethyl-substituted tetrathiafulvalenes

• Olivier Jeannin,
• Frédéric Barrière and
• Marc Fourmigué

Beilstein J. Org. Chem. 2015, 11, 647–658, doi:10.3762/bjoc.11.73

• introduced on the dithiole ring upon substitution with the CN and CO2Me (−M) EWG are not offset by the competing CF3 group, confirming its much weaker mesomeric effect on the conjugated dithiole core. Optical properties and theoretical calculations have shown that the HOMO–LUMO gap is not much modified in

Enhancing the reactivity of 1,2-diphospholes in cycloaddition reactions

• Almaz Zagidullin,
• Vasili Miluykov,
• Elena Oshchepkova,
• Artem Tufatullin,
• Olga Kataeva and
• Oleg Sinyashin

Beilstein J. Org. Chem. 2015, 11, 169–173, doi:10.3762/bjoc.11.17

• theoretical calculations and experimental work [7][8]. At the same time both the presence of the P=C bond in phospholes as well as the transient 2H-phospholes [3] increase the cycloaddition reactivity. It was previously demonstrated that 1-alkyl-1,2-diphospholes combine the properties of both 1H-phospholes

Solution processable diketopyrrolopyrrole (DPP) cored small molecules with BODIPY end groups as novel donors for organic solar cells

• Diego Cortizo-Lacalle,
• Calvyn T. Howells,
• Upendra K. Pandey,
• Joseph Cameron,
• Neil J. Findlay,
• Anto Regis Inigo,
• Tell Tuttle,
• Peter J. Skabara and
• Ifor D. W. Samuel

Beilstein J. Org. Chem. 2014, 10, 2683–2695, doi:10.3762/bjoc.10.283

• as the conjugation increases (95 and 97 nm), with compound 10 giving two peaks at 607 and 645 nm. Theoretical calculations support the assignment of these absorption bands to the π–π* transition which is localised on the DPP core (vide infra). Optical HOMO–LUMO gaps in solution were calculated from

• –LUMO gap to the same extent. The aggregation of 9 in the solid state results in a decrease of the energy gap making it appear similar to 10, even if the conjugation length is shorter [49]. Theoretical calculations DFT optimisations were carried out for compounds 9 and 10, with the optimised structures

• microscopy (AFM). Theoretical calculations DFT optimisations were carried out in TURBOMOLE 6.3.1 [57] using B97-D [58] functional with def2-TZVP [59] basis set in dichloromethane using COSMO [60] solvent model. RI-J [61] approximation was implemented for these optimisations. TDDFT [62] and CHelpG [51