Water-soluble host–guest complexes between fullerenes and a sugar-functionalized tribenzotriquinacene assembling to microspheres

• Si-Yuan Liu,
• Xin-Rui Wang,
• Man-Ping Li,
• Wen-Rong Xu and
• Dietmar Kuck

Beilstein J. Org. Chem. 2020, 16, 2551–2561, doi:10.3762/bjoc.16.207

• diffraction. Therefore, the optimized geometry of the 1:1 complex of TBTQ-(OG)6 C60 in water was simulated by density functional theory (DFT) calculations at the B3LYP/6-31G(d) level of theory, which was completed with the aid of Molclus, MOPAC, and ORCA 4.1.0 programs [54][55][56]. As shown in Figure 6, C60

Conformational preferences of fluorine-containing agrochemicals and their implications for lipophilicity prediction

• Daniela Rodrigues Silva,
• Joyce K. Daré and
• Matheus P. Freitas

Beilstein J. Org. Chem. 2020, 16, 2469–2476, doi:10.3762/bjoc.16.200

• high degree of freedom in the chemical structure of penoxsulam (I), the conformational analysis started with a Monte Carlo conformational search at the ωB97X-D/6-31G(d,p) [16][17] level of the density functional theory (DFT). The global energy minimum conformation was then re-optimized in a higher

Styryl-based new organic chromophores bearing free amino and azomethine groups: synthesis, photophysical, NLO, and thermal properties

• Anka Utama Putra,
• Deniz Çakmaz,
• Nurgül Seferoğlu,
• Alberto Barsella and
• Zeynel Seferoğlu

Beilstein J. Org. Chem. 2020, 16, 2282–2296, doi:10.3762/bjoc.16.189

• series of new styryl-based organic chromophores containing a free amino group and the corresponding Schiff base derivatives. The photophysical, pH sensitivity, NLO properties, and thermal stabilities of all synthesized dyes were investigated. Density Functional Theory (DFT) calculations were also

Synthetic approaches to bowl-shaped π-conjugated sumanene and its congeners

• Shakeel Alvi and
• Rashid Ali

Beilstein J. Org. Chem. 2020, 16, 2212–2259, doi:10.3762/bjoc.16.186

• thermoelectric properties in addition to the onigiri-type core-shell assemblies have been reported for sumanene and its derivatives. More interestingly, its application in the absorption of small molecules such as NH3, CO2, CO, and H2 using density functional theory (DFT) calculations has also been revealed [25

• /mol) transformation of 12 (syn) to 17, calculated by density functional theory (DFT) calculations. On the other hand, in 2008, Higashibayashi et al. reported the synthesis of first chiral C3-symmetric trimethylsumanene 28 starting from enantiopure norbornadiene (10) by employing a rational synthetic

• an LED lamp at ca. 365 nm for 1 min in 2-methyltetrahydrofuran (mTHF) at 77 K gave 60 (Scheme 13) [45]. It was noticed from both experimental as well as theoretical studies that the ground state of the prepared carbene 60 is a triplet which was confirmed by ESR as well as density functional theory

Muyocopronones A and B: azaphilones from the endophytic fungus Muyocopron laterale

• Ken-ichi Nakashima,
• Junko Tomida,
• Tomoe Tsuboi,
• Yoshiaki Kawamura and
• Makoto Inoue

Beilstein J. Org. Chem. 2020, 16, 2100–2107, doi:10.3762/bjoc.16.177

• ) [25]. After conformational analysis, geometry optimization was performed for two possible stereoisomers with the (7S,10R,11R)- and (7S,10S,11S)-configurations using density functional theory (DFT) at the CAM-B3LYP/6-311+G(d,p) level of theory. In addition, the ECD spectra of the DFT-optimized

One-pot synthesis of oxazolidinones and five-membered cyclic carbonates from epoxides and chlorosulfonyl isocyanate: theoretical evidence for an asynchronous concerted pathway

• Esra Demir,
• Ozlem Sari,
• Yasin Çetinkaya,
• Ufuk Atmaca,
• Safiye Sağ Erdem and
• Murat Çelik

Beilstein J. Org. Chem. 2020, 16, 1805–1819, doi:10.3762/bjoc.16.148

• advantageous: being a one-pot reaction with metal-free reagent, having shorter reaction times, good yields and a very simple purification method. Moreover, using the density functional theory (DFT) method at the M06-2X/6-31+G(d,p) level of theory the mechanism of the cycloaddition reactions has been elucidated

Rearrangement of o-(pivaloylaminomethyl)benzaldehydes: an experimental and computational study

• Csilla Hargitai,
• Györgyi Koványi-Lax,
• Tamás Nagy,
• Péter Ábrányi-Balogh,
• András Dancsó,
• Gábor Tóth,
• Judit Halász,
• Angéla Pandur,
• Gyula Simig and
• Balázs Volk

Beilstein J. Org. Chem. 2020, 16, 1636–1648, doi:10.3762/bjoc.16.136

• reaction described in Scheme 1 to further o-(pivaloylaminomethyl)benzaldehydes and to support the results by density functional theory (DFT) calculations, single-crystal X-ray measurements and comprehensive NMR studies. Results and Discussion Acid-catalyzed transformations of compounds 1a–d First we kept

Heterogeneous photocatalysis in flow chemical reactors

• Christopher G. Thomson,
• Ai-Lan Lee and
• Filipe Vilela

Beilstein J. Org. Chem. 2020, 16, 1495–1549, doi:10.3762/bjoc.16.125

• measurements, TRPL spectroscopy, and density functional theory (DFT) calculations. They found that the HER efficiency correlated to the excited state lifetime and exciton binding energy. The FSO-BP and FSO-FSz hindered the charge transfer and mobility due to the phenyl–phenyl dihedral angle or sharp bends in

In silico rationalisation of selectivity and reactivity in Pd-catalysed C–H activation reactions

• Liwei Cao,
• Mikhail Kabeshov,
• Steven V. Ley and
• Alexei A. Lapkin

Beilstein J. Org. Chem. 2020, 16, 1465–1475, doi:10.3762/bjoc.16.122

• the mechanistic models based on accurate quantum chemical methods, such as the density functional theory (DFT) methods, decreases. Automation of DFT, as well as using results of DFT to develop less expensive predictive models, are the two approaches that may offer the alternatives to the fully data

• transition metal coordination sphere; the energy of a new M–C bond formed and the thermodynamic stability of organometallic product. With new developments in computational chemistry, mechanistic studies using density functional theory (DFT) provide valuable insights into the reactivity of organometallic

Development of fluorinated benzils and bisbenzils as room-temperature phosphorescent molecules

• Shigeyuki Yamada,
• Takuya Higashida,
• Yizhou Wang,
• Masato Morita,
• Takuya Hosokai,
• Kaveendra Maduwantha,
• Kaveenga Rasika Koswattage and
• Tsutomu Konno

Beilstein J. Org. Chem. 2020, 16, 1154–1162, doi:10.3762/bjoc.16.102

• -deficient fluorinated aromatic ring. To confirm the electron-withdrawing effect of this fluorinated aromatic ring, the electronic charge at the adjacent C≡C bond was calculated by density functional theory (DFT) using the Gaussian 16 (Revision B.01) software package [35]. As typical examples, the molecular

• molecular orbitals (isosurface value: 0.04 a.u.) involved in vertical electronic transitions in 2a and 3a calculated using density functional theory (DFT) and time-dependent DFT at the CAM-B3LYP/6-31+G(d) level (HOMO: highest occupied molecular orbital, LUMO: lowest unoccupied molecular orbital). Synthetic

Aryl-substituted acridanes as hosts for TADF-based OLEDs

• Naveen Masimukku,
• Dalius Gudeika,
• Oleksandr Bezvikonnyi,
• Ihor Syvorotka,
• Rasa Keruckiene,
• Dmytro Volyniuk and
• Juozas V. Grazulevicius

Beilstein J. Org. Chem. 2020, 16, 989–1000, doi:10.3762/bjoc.16.88

• . Theoretical calculations The optimized structures of 3–6 were obtained by density functional theory (DFT) calculations at the B3LYP/6-31G(d,p) level of theory (Figure 1). The dihedral angles between the acridanyl and phenyl moieties in compound 3 (37.0 and 36.3°) are comparable with the dihedral angles

Cation-induced ring-opening and oxidation reaction of photoreluctant spirooxazine–quinolizinium conjugates

• Phil M. Pithan,
• Sören Steup and
• Heiko Ihmels

Beilstein J. Org. Chem. 2020, 16, 904–916, doi:10.3762/bjoc.16.82

• discussed in the literature whether metal cations are coordinated in a monodentate fashion to the phenolate oxygen atom or rather in a bidentate fashion both to the phenolate oxygen and the imine nitrogen atoms of the open merocyanine form [25][28]. Furthermore, density functional theory (DFT) calculations

Direct borylation of terrylene and quaterrylene

• Haruka Kano,
• Keiji Uehara,
• Kyohei Matsuo,
• Hironobu Hayashi,
• Hiroko Yamada and
• Naoki Aratani

Beilstein J. Org. Chem. 2020, 16, 621–627, doi:10.3762/bjoc.16.58

• fluorescence at 576 nm with a quantum yield of ΦF = 0.86 at 298 K (Figure 3). Both peaks are slightly red-shifted relative to those of intact terrylene (λabs = 560 nm and λem = 571 nm with ΦF = 0.82 in toluene). We employed density functional theory (DFT) and time-dependent (TD)-DFT calculations, both of them

Regioselectively α- and β-alkynylated BODIPY dyes via gold(I)-catalyzed direct C–H functionalization and their photophysical properties

• Takahide Shimada,
• Shigeki Mori,
• Masatoshi Ishida and
• Hiroyuki Furuta

Beilstein J. Org. Chem. 2020, 16, 587–595, doi:10.3762/bjoc.16.53

• , density functional theory (DFT) calculations were performed at the B3LYP/6-31G(d) level of theory. The a2-symmetry of the HOMOs and b2-symmetry of the LUMOs of each, the α- and β-ethynyl-substituted BODIPYs are almost identical to those of the unsubstituted compound 1a (Figure S24, Supporting Information

Six-fold C–H borylation of hexa-peri-hexabenzocoronene

• Mai Nagase,
• Kenta Kato,
• Akiko Yagi,
• Yasutomo Segawa and
• Kenichiro Itami

Beilstein J. Org. Chem. 2020, 16, 391–397, doi:10.3762/bjoc.16.37

• hexaborylated HBC 1. The structure of thus-obtained 1 was confirmed by X-ray crystallography, and the electronic effects of the boryl groups were investigated through optoelectronic measurements and density functional theory (DFT) calculations. Results and Discussion We have examined the conditions for C–H

p-Pyridinyl oxime carbamates: synthesis, DNA binding, DNA photocleaving activity and theoretical photodegradation studies

• Panagiotis S. Gritzapis,
• Panayiotis C. Varras,
• Nikolaos-Panagiotis Andreou,
• Katerina R. Katsani,
• Konstantinos Dafnopoulos,
• George Psomas,
• Zisis V. Peitsinis,
• Alexandros E. Koumbis and
• Konstantina C. Fylaktakidou

Beilstein J. Org. Chem. 2020, 16, 337–350, doi:10.3762/bjoc.16.33

• factor of 1.43 [11]. Theoretical calculations Calculations for the photodegradation of carbamates The structures, properties and the basic photochemistry of compounds 11 and 12 was studied using the density functional theory (DFT) method [86][87][88][89] and the functional B3PW91 along with the 6-31 G(d

The reaction of arylmethyl isocyanides and arylmethylamines with xanthate esters: a facile and unexpected synthesis of carbamothioates

• Narasimhamurthy Rajeev,
• Toreshettahally R. Swaroop,
• Ahmad I. Alrawashdeh,
• Shofiur Rahman,
• Abdullah Alodhayb,
• Seegehalli M. Anil,
• Kuppalli R. Kiran,
• Chandra,
• Paris E. Georghiou,
• Kanchugarakoppal S. Rangappa and
• Maralinganadoddi P. Sadashiva

Beilstein J. Org. Chem. 2020, 16, 159–167, doi:10.3762/bjoc.16.18

• , however, carbamothioates 4a–l were instead obtained in 76–88% yield (Scheme 1). Herein, we report on this intriguing finding and show several examples, including a single crystal X-ray structure of one of the products so obtained. A plausible mechanism to explain the reaction using density functional

• theory (DFT) analysis is also presented in this article. Results and Discussion Synthesis At the onset of our study, the reaction between O-benzyl S-methyl dithiocarbonate (1a) and benzyl isocyanide was conducted in the presence of sodium hydride in DMF. The product, obtained in 85% yield after 10 min

Synthesis and characterization of bis(4-amino-2-bromo-6-methoxy)azobenzene derivatives

• David Martínez-López,
• Amirhossein Babalhavaeji,
• Diego Sampedro and
• G. Andrew Woolley

Beilstein J. Org. Chem. 2019, 15, 3000–3008, doi:10.3762/bjoc.15.296

• absorption wavelengths of possible derivatives. Based on these considerations, we carried out the synthesis and photochemical characterization of compounds 4 and 5. Results and Discussion Computational chemistry Calculations were performed using density functional theory (DFT) methods (B3LYP/6-31+G**) to

Synthesis and optoelectronic properties of benzoquinone-based donor–acceptor compounds

• Daniel R. Sutherland,
• Nidhi Sharma,
• Georgina M. Rosair,
• Ifor D. W. Samuel,
• Ai-Lan Lee and
• Eli Zysman-Colman

Beilstein J. Org. Chem. 2019, 15, 2914–2921, doi:10.3762/bjoc.15.285

• carbazoles with respect to the bridging benzene of ca. 44° in both 3 and 4 (Figure 2). Theoretical properties Density functional theory (DFT) calculations were performed in the gas phase to assess the electronic structures of 2–5 (see Supporting Information File 1 for details). The S1 and T1 excited states

A combinatorial approach to improving the performance of azoarene photoswitches

• Joaquin Calbo,
• Aditya R. Thawani,
• Rosina S. L. Gibson,
• Andrew J. P. White and
• Matthew J. Fuchter

Beilstein J. Org. Chem. 2019, 15, 2753–2764, doi:10.3762/bjoc.15.266

• performance: o-F [13][14], o-Cl [8][29][30], o-OMe [10][29][31], or o-Pyr [32]. For the sake of comparison, both mono- and di-ortho-substitutions were considered. Theoretical half-lives (t1/2) were calculated within the density functional theory (DFT) framework, according to the protocol reported in our prior

Experimental and computational electrochemistry of quinazolinespirohexadienone molecular switches – differential electrochromic vs photochromic behavior

• Eric W. Webb,
• Jonathan P. Moerdyk,
• Kyndra B. Sluiter,
• Benjamin J. Pollock,
• Amy L. Speelman,
• Eugene J. Lynch,
• William F. Polik and
• Jason G. Gillmore

Beilstein J. Org. Chem. 2019, 15, 2473–2485, doi:10.3762/bjoc.15.240

• functional theory (DFT) calculated molecular orbitals (MOs, e.g., Figure 6 and Supporting Information File 1) indicate that the LUMO (MO 106 for 3a) lies exclusively on the dienone moiety both in 1b and in the quinazolinespirohexadienone photochromes 3a,b. Thus, the dienone moiety is likely the electrophore

• deviation in the experimental measurements. This demonstrates that the computational correlation employed is useful in structural assignment and accurate within a standard of error of the experimental reduction potentials of these spirohexadienones’ different constitutional SW and LW isomers. Density

Reversible switching of arylazopyrazole within a metal–organic cage

• Anton I. Hanopolskyi,
• Soumen De,
• Michał J. Białek,
• Yael Diskin-Posner,
• Liat Avram,
• Moran Feller and
• Rafal Klajn

Beilstein J. Org. Chem. 2019, 15, 2398–2407, doi:10.3762/bjoc.15.232

• -ray diffraction. To obtain hints about the packing of Z-1 within 2, we therefore performed density functional theory (DFT) calculations. Compared with the complex before photoisomerization, the cage in (Z-1)2 is severely distorted (Figure 5; see also Supporting Information File 3), assuming a bowl

Current understanding and biotechnological application of the bacterial diterpene synthase CotB2

• Ronja Driller,
• Daniel Garbe,
• Norbert Mehlmer,
• Monika Fuchs,
• Keren Raz,
• Dan Thomas Major,
• Thomas Brück and
• Bernhard Loll

Beilstein J. Org. Chem. 2019, 15, 2355–2368, doi:10.3762/bjoc.15.228

• rearrangement. Hong and Tantillo performed the first theoretical study of the reaction mechanism in CotB2 via gas phase density functional theory (DFT) calculations [33]. Simultaneously, Sato et al. also studied the CotB2 reaction mechanism in the gas phase using DFT, combined with experimental deuterium

Aggregation-induced emission effect on turn-off fluorescent switching of a photochromic diarylethene

• Luna Kono,
• Yuma Nakagawa,
• Ayako Fujimoto,
• Ryo Nishimura,
• Yohei Hattori,
• Toshiki Mutai,
• Nobuhiro Yasuda,
• Kenichi Koizumi,
• Satoshi Yokojima,
• Shinichiro Nakamura and
• Kingo Uchida

Beilstein J. Org. Chem. 2019, 15, 2204–2212, doi:10.3762/bjoc.15.217

• functional theory (DFT) and time-dependent DFT (TDDFT). The excitation wavelengths as well as the emission wavelength qualitatively agrees with the experimental results. Since compound 1 consists of a diarylethene moiety and an imidazo[1,2-a]pyridine moiety, the characteristic of 1 has the combination of

• decreased gradually upon UV light irradiation accompanied with the formation of 1c, because of excitation energy transfer from the ESIPT moiety to the closed-ring isomer (Figure 5) [4]. The wavelengths of absorption (Table 3) and fluorescence (Table 4) were obtained computationally by using density

Azologization and repurposing of a hetero-stilbene-based kinase inhibitor: towards the design of photoswitchable sirtuin inhibitors

• Christoph W. Grathwol,
• Nathalie Wössner,
• Sören Swyter,
• Adam C. Smith,
• Enrico Tapavicza,
• Robert K. Hofstetter,
• Anja Bodtke,
• Manfred Jung and
• Andreas Link

Beilstein J. Org. Chem. 2019, 15, 2170–2183, doi:10.3762/bjoc.15.214

• functional theory (DFT) to optimize the ground state equilibrium structures of (E)-2b, (Z)-2b, 8a and 8b, and used time-dependent DFT (TDDFT) and high-level correlated methods to obtain UV–vis absorption energies and oscillator strengths. To obtain the simulated absorption spectrum and λmax values

• ortho methyl groups in 2f, intramolecular photocyclization could be prevented. To verify the hypothetical structures derived from irradiation of 2b, we carried out quantum chemical calculations of the double bond isomers (E)-2b and (Z)-2b as well as the oxidized compounds 8a and 8b. We used density