Optimizing reaction conditions for the light-driven hydrogen evolution in a loop photoreactor

• Pengcheng Li,
• Daniel Kowalczyk,
• Johannes Liessem,
• Mohamed M. Elnagar,
• Dariusz Mitoraj,
• Radim Beranek and
• Dirk Ziegenbalg

Beilstein J. Org. Chem. 2024, 20, 74–91, doi:10.3762/bjoc.20.9

• 560 rpm. Red channel values of ROIs with different stirring speeds: (a) left space between reactor and draft tube, (b) in draft tube, (c) right space between reactor and draft tube. Quantified mixing time using different stirring speeds. Chemical actinometry results: (a) actinometer conversion at

• different irradiation time, (b) photon flux at different irradiation time. Photon flux in the loop reactor with respect to the LED electrical current. Absorbance as function of photocatalyst loading for different optical path lengths. Long-term operation of the loop photoreactor. Visualization of the

• response surfaces of the modified DOE model for the four parameters: (a) photon flux and inert gas flow rate, (b) photocatalyst loading and stirring speed. Parity plot of the measured photocatalytic hydrogen generation rate versus the values predicted by the models from DOE analysis. Effect of photon flux

Multi-redox indenofluorene chromophores incorporating dithiafulvene donor and ene/enediyne acceptor units

• Christina Schøttler,
• Kasper Lund-Rasmussen,
• Line Broløs,
• Philip Vinterberg,
• Ema Bazikova,
• Viktor B. R. Pedersen and
• Mogens Brøndsted Nielsen

Beilstein J. Org. Chem. 2024, 20, 59–73, doi:10.3762/bjoc.20.8

• Christina Schottler Kasper Lund-Rasmussen Line Brolos Philip Vinterberg Ema Bazikova Viktor B. R. Pedersen Mogens Brondsted Nielsen Department of Chemistry, University of Copenhagen, Universitetsparken 5 DK-2100 Copenhagen Ø, Denmark Sino-Danish College (SDC), University of Chinese Academy of

• the introduction of an indeno[1,2-b]fluorene (IF) core [13], providing indenofluorene-extended TTFs (IF-TTFs) of the general structure shown in Figure 1. The π-system can be further expanded as well at the dithiole rings. For example, we have recently developed a synthetic protocol for fusing a

• lengths of the bonds (b–f) within the five-membered rings of the cores as well as the exocyclic C=C double bond (a) that is present in compounds 25 and 26 (for bond labels, see Figure 11). A small difference in the exocyclic C=C bond length is observed between 25 and 26, with the bond in 26 being slightly

Preparing a liquid crystalline dispersion of carbon nanotubes with high aspect ratio

• Keiko Kojima,
• Nodoka Kosugi,
• Hirokuni Jintoku,
• Kazufumi Kobashi and
• Toshiya Okazaki

Beilstein J. Org. Chem. 2024, 20, 52–58, doi:10.3762/bjoc.20.7

• dispersion. The polarizing optical microscopy (POM) images exhibited alignment of the DWCNTs along the shear direction (Figure 4a,b). To estimate the order parameter, the polarized optical absorption measurement was conducted at different sample angles ranging from 0° to 90° at intervals of 10° (Figure 4c

• -770 spectrometer. The film's thicknesses were measured using a laser confocal microscope (OLYMPUS, OLS-4500). (a) Size distribution of DWCNTs in dispersion by DCS measurements. (b) Optical microscopy image of the DWCNT dispersion. Scale bar is 100 µm. (a) Phase diagram of the DWCNT dispersion. The

• nematic phase, biphasic state and isotropic phase are marked by filled circle, open circle and cross mark, respectively. (b-d) POM images of the dispersions. DWCNT concentrations are (b) 0.41 vol %, (c) 0.16 vol % and (d) 0.078 vol %. Scale bars are 200 µm. (e) The plot of the phase transition

Using the phospha-Michael reaction for making phosphonium phenolate zwitterions

• Matthias R. Steiner,
• Max Schmallegger,
• Larissa Donner,
• Johann A. Hlina,
• Christoph Marschner,
• Judith Baumgartner and
• Christian Slugovc

Beilstein J. Org. Chem. 2024, 20, 41–51, doi:10.3762/bjoc.20.6

• acceptor methyl acrylate reacts much faster in chloroform than acrylonitrile. A likely explanation is the preorganization of the Michael acceptor and donor by hydrogen bonding between the phosphine’s hydroxy group and the carbonyl group of the ester B’. Such a preorganization facilitates the proton

• transfer [34] from the hydroxy group to the initial zwitterion via B’’ and B’’’ resulting in C. In this case, the proton at the α-position to the electron-withdrawing group is stemming from the phenol moiety. Methyl acrylate in methanol is the fastest reaction presumably because both pathways, the

• intramolecular proton transfer and the methanol-mediated proton transfer, can occur. It has been described that intermediate B is more stable with enolizable electron-withdrawing groups such as esters [50] when compared to, e.g., a nitrile [49]. Accordingly, the intermolecular proton transfer pathway should be

Facile access to pyridinium-based bent aromatic amphiphiles: nonionic surface modification of nanocarbons in water

• Lorenzo Catti,
• Shinji Aoyama and
• Michito Yoshizawa

Beilstein J. Org. Chem. 2024, 20, 32–40, doi:10.3762/bjoc.20.5

• similar to AA [12][13], indicating self-assembly via the hydrophobic effect and π-stacking interactions (Figure 3a,b). The self-assembly in water was further supported by UV–visible analysis, displaying slight red-shifts of the anthracene absorption bands relative to the spectrum in methanol (Δλmax = +3

• protons upon addition of HCl (40 equiv based on PA-Im; Figure 5a,b). These properties enabled a pH-responsive surface charge of its host–guest composite (Table 2). Accordingly, (PA-Im)n·(C60)m displayed a ZP of 60.3 mV at pH 2.8 contrary to 52.8 mV at pH 6.8 (ΔZP = +7.5 mV) [26]. Control experiments using

• -solubilization and modification of nanocarbons (NCs). b) Bent aromatic amphiphiles AA and PA-R (R = CH3 and CH2CH2(OCH2CH2)2–Y (Y = OCH3, OH, and imidazole)). c) Nonionic surface modification of NCs via noncovalent encircling with PA-Rs. a) Synthetic route toward prePA and PA-CH3, including the optimized

Cycloaddition reactions of heterocyclic azides with 2-cyanoacetamidines as a new route to C,N-diheteroarylcarbamidines

• Pavel S. Silaichev,
• Tetyana V. Beryozkina,
• Vsevolod V. Melekhin,
• Valeriy O. Filimonov,
• Andrey N. Maslivets,
• Vladimir G. Ilkin,
• Wim Dehaen and
• Vasiliy A. Bakulev

Beilstein J. Org. Chem. 2024, 20, 17–24, doi:10.3762/bjoc.20.3

• and Molecules, Department of Chemistry, KU Leuven, Celestijnenlaan 200F, B-3001 Leuven, Belgium 10.3762/bjoc.20.3 Abstract A novel and efficient base-catalyzed, transition-metal-free method for the synthesis of diheterocyclic compounds connected by an amidine linker, including apart from the common

• moderate to high yields (46–98%), ranging between 79–98% for reactions of 3,3-diaminoacrylonitriles 1 with azidoheterocycles 2. Compared with azidopyrimidines 2a,b and azidochromene 2g, the use of azidoazoles 2c–f delivered the expected amidines 3l–r in somewhat lower yields. No definite electronic effect

• mL) was added and the resulting solution was stirred for additional 5 min. Then, acetic acid (34 µL) was added to the reaction mixture, the formed precipitate was filtered off, washed with water, and dried in a desiccator over P4O10. Method B. Amidine 1 (0.5 mmol) was added into a solution of sodium

Synthesis of N-acyl carbazoles, phenoxazines and acridines from cyclic diaryliodonium salts

• Nils Clamor,
• Mattis Damrath,
• Thomas J. Kuczmera,
• Daniel Duvinage and
• Boris J. Nachtsheim

Beilstein J. Org. Chem. 2024, 20, 12–16, doi:10.3762/bjoc.20.2

• nitrile-substituted carbazoles 2s and 2t, which are potent fluorophores. While 2s was isolated in 61% yield, the additional 6-bromo-substituent diminished the yield of 2t to 47%. When we subjected 6-membered 10H-dibenzo[b,e]iodinin-5-iums to our conditions, we synthesized the N-acyl dihydroacridane 3a

• with a 47% yield. A method for the synthesis of similar annulated N-heterocycles from iodanes with nitriles is described by Chen et al. [34]. Next, we investigated O-bridged dibenzo[b,e][1,4]iodaoxin-5-ium salts as substrates, as was shown in a recent work [29]. Following the trend, we already observed

• equiv amide, 15 mol % CuI, 30 mol % diglyme, 3.00 equiv K2CO3 and 2.00 equiv dibenzo[b,d]iodol-5-ium trifluoromethanesulfonate. Scope of iodanes. aIsolated yields, 200 µmol scale, all reactions carried out in p-xylene, with 1.00 equiv amide 15 mol % CuI, 30 mol % diglyme, 3.00 equiv K2CO3 and 2.00 equiv

Identification of the p-coumaric acid biosynthetic gene cluster in Kutzneria albida: insights into the diazotization-dependent deamination pathway

• Seiji Kawai,
• Akito Yamada,
• Yohei Katsuyama and
• Yasuo Ohnishi

Beilstein J. Org. Chem. 2024, 20, 1–11, doi:10.3762/bjoc.20.1

• ) and 3-aminoavenalumic acid (7) were synthesized in our previous study [13]. Construction of heterologous expression vectors First, pHKO4-cmaI-D was constructed by cloning the cmaI-H-A1-A2-A3-A4-A5-A6-B-A7-E-D operon (which was amplified by PCR using K. albida genomic DNA as the template) into the NdeI

• harbor similar gene components except for the genes encoding oxidoreductases (avaA8 and cmaG), transporter (avaC), and regulator (cmaR). B) The proposed biosynthetic pathway of p-coumaric acid by the cma cluster. Heterologous expression of the cma cluster in S. albus. A) Schematic representation of the

• gene sets on heterologous expression plasmids to construct S. albus-cma. The tipA promoter was used for gene expression. B) Metabolite analysis of S. albus-cma. UV chromatograms at 310 nm are shown. The production yield of 6 was decreased in S. albus-cma ∆cmaG. Several metabolites produced by S. albus

1-Butyl-3-methylimidazolium tetrafluoroborate as suitable solvent for BF₃: the case of alkyne hydration. Chemistry vs electrochemistry

• Marta David,
• Elisa Galli,
• Richard C. D. Brown,
• Marta Feroci,
• Fabrizio Vetica and
• Martina Bortolami

Beilstein J. Org. Chem. 2023, 19, 1966–1981, doi:10.3762/bjoc.19.147

• literature for BMIm-F [110]. The only difference between IL 19F NMR spectra before and after electrolysis is a peak at ‒148.7 ppm (referred to BF4− at −150.6 ppm), possibly due to BF3OH− or B2F7− [111][112] (see Supporting Information File 1, Figure S1a vs f and b, c). This last hypothesis is corroborated by

• neat anolyte was analysed by NMR (19F and 13C). A peak at 166.0 ppm in the 13C NMR spectrum appeared and no traces of starting DBU (peak at 161 ppm) were evidenced (see Supporting Information File 1, Figure S5a, b and d). As regards the 19F NMR spectrum, a new peak at −148.6 ppm appeared, consistent

Long oligodeoxynucleotides: chemical synthesis, isolation via catching-by-polymerization, verification via sequencing, and gene expression demonstration

• Yipeng Yin,
• Reed Arneson,
• Alexander Apostle,
• Adikari M. D. N. Eriyagama,
• Komal Chillar,
• Emma Burke,
• Martina Jahfetson,
• Yinan Yuan and
• Shiyue Fang

Beilstein J. Org. Chem. 2023, 19, 1957–1965, doi:10.3762/bjoc.19.146

• compared with the authentic dsODNs using agarose gel electrophoresis (steps 3 and 3', Figure 1). As shown in Figure 2A,B, the synthesized and authentic samples have similar migration distances. The identity of the ODNs was then determined by Sanger sequencing. The PCR products were cloned into the pCR

• for the construction, verification, and expression of the 800 bp GFP gene from chemically synthesized long ODNs. (a) Sequence analysis via gel electrophoresis by comparing with control ODNs (see Figure 2A,B). (b) Sequence analysis via colony PCR, gel electrophoresis (see Figure 3), and Sanger

• sequencing. (c) Sequence analysis via transforming NEB® 5-alpha cells, colony PCR, gel electrophoresis (Figure 2C), and Sanger sequencing. CBP, catching-by-polymerization. GFP, green fluorescent protein. nt, nucleotide. PCR, polymerase chain reaction. Gel electrophoresis images of 399 bp (A), 401 bp (B), and

Construction of diazepine-containing spiroindolines via annulation reaction of α-halogenated N-acylhydrazones and isatin-derived MBH carbonates

• Xing Liu,
• Wenjing Shi,
• Jing Sun and
• Chao-Guo Yan

Beilstein J. Org. Chem. 2023, 19, 1923–1932, doi:10.3762/bjoc.19.143

• sequentially underwent a [4 + 3] cycloaddition reaction (reaction 1 in Scheme 1) [54]. Recently, Chen and co-workers reported a chiral tertiary amine-catalyzed asymmetric γ-regioselective [4 + 3] annulation reaction of isatin-derived MBH carbonates and cyclic 2-benzylidenebenzo[b]thiophen-3-ylidene

• )benzenesulfonamides to give chiral azepane spirooxindoles with excellent stereoselectivity (reaction 2 in Scheme 1) [55][56]. Du and co-workers reported a DABCO-mediated [4 + 3] cycloaddition reaction between o-quinone methides and isatin-derived MBH carbonates to give functionalized benzo[b]oxepine derivatives in

• satisfactory yields and with good diastereoselectivity (reaction 3, Scheme 1) [57]. Very recently, we found that the base-catalyzed [4 + 3] cycloaddition reaction of isatin-derived MBH carbonates with various α,β-unsaturated N-arylaldimines affords spiro[indoline-3,5'-pyrrolo[3,4-b]azepine] derivatives

Beyond n-dopants for organic semiconductors: use of bibenzo[d]imidazoles in UV-promoted dehalogenation reactions of organic halides

• Kan Tang,
• Megan R. Brown,
• Chad Risko,
• Melissa K. Gish,
• Garry Rumbles,
• Phuc H. Pham,
• Oana R. Luca,
• Stephen Barlow and
• Seth R. Marder

Beilstein J. Org. Chem. 2023, 19, 1912–1922, doi:10.3762/bjoc.19.142

• in THF are ca. 420 and 43 M−1 cm−1, respectively. Figure 3a and b show the absorption spectra of the two dimeric reductants in THF (see Supporting Information File 1, Figure S6 for data in toluene). (N-DMBI)2 shows a strong absorption feature with a maximum at 304 nm (εmax = 28000 M−1 cm−1) and a

• to the more strongly reducing monomers, which may help inform the use of these and related reductants in achieving other chemical transformations. (a, b) Schematics of previous approaches to dehalogenation-based reactions using molecular reductants, along with representative structures of reductants

• representative temporal evolution of % conversion (blue squares), % toluene yield (red diamonds), and % bibenzyl yield (black circles) during the dark dehalogenation reaction of benzyl bromide (BnBr) using (N-DMBI)2 in THF (these data were acquired using 3 mM BnBr and 1.5 mM of (N-DMBI)2. (b) Plot of [D2]0

Biphenylene-containing polycyclic conjugated compounds

• Cagatay Dengiz

Beilstein J. Org. Chem. 2023, 19, 1895–1911, doi:10.3762/bjoc.19.141

• subjecting α,α,α′,α′-tetrabromo-o-xylene (16) to t-BuOK to anhydrous conditions, biphenylene derivative 17 was obtained with a yield of 69% (Scheme 3). In the final step of the synthesis, a halogen–lithium exchange was carried out, followed by treatment with MeOH, resulting in a 79% yield of benzo[b

• ]biphenylene (18). In their efforts to find a more general method for the synthesis of benzo[b]biphenylenes, Barton and co-workers were able to synthesize benzo[b]biphenylene (18) in 71% yield by the reaction of equal molar amounts of tetrabromo compound 16 and 1,1,2,2-tetrabromo-1,2-dihydrobenzocyclobutene

• reactions involving 1,4-dibromo-2,5-dichlorobenzene (31) and substituted oxanorbornenes (26 and 30b,c), products 32a–c, with R groups representing (a) H, (b) F, and (c) –OCH2O–, were successfully synthesized, albeit with moderate yields (Scheme 7). Following that, compounds 32a–c underwent derivatization

Anion–π catalysis on carbon allotropes

• M. Ángeles Gutiérrez López,
• Mei-Ling Tan,
• Giacomo Renno,
• Augustina Jozeliūnaitė,
• J. Jonathan Nué-Martinez,
• Javier Lopez-Andarias,
• Naomi Sakai and
• Stefan Matile

Beilstein J. Org. Chem. 2023, 19, 1881–1894, doi:10.3762/bjoc.19.140

• catalysis. Moreover, epoxide opening polyether cyclizations are among the most impressive cascade reactions in nature [71][72][73]. Best known is the hypothetical cascade XII in the biosynthesis of brevetoxin B [74]. It affords eleven fused ethers by violating the Eschenmoser–Dunitz–Baldwin guidelines [75

• -covalently electrify organic synthesis in the broadest sense. (A) Anion–π catalysis: Stabilization of anionic transition states from substrate S to product P on π-acidic aromatic surfaces. (B) Anion–(π)n–π catalysis: Stabilization of anionic transition states by polarization of π stacks to induce oriented

• catalysts other than carbon allotropes. (A) Macrodipoles induced by anionic transition states account for anion–π catalysis on fullerenes. (B) Fullerene dimers double polarizability of the π system and thus anion–π catalysis, with structure of fullerene dimer 37, intercalating activators and inactivators

Aromatic systems with two and three pyridine-2,6-dicarbazolyl-3,5-dicarbonitrile fragments as electron-transporting organic semiconductors exhibiting long-lived emissions

• Karolis Leitonas,
• Brigita Vigante,
• Dmytro Volyniuk,
• Audrius Bucinskas,
• Pavels Dimitrijevs,
• Sindija Lapcinska,
• Pavel Arsenyan and
• Juozas Vidas Grazulevicius

Beilstein J. Org. Chem. 2023, 19, 1867–1880, doi:10.3762/bjoc.19.139

• -carbonitrile (REF) [5]. Absorption spectra of dilute toluene, tetrahydrofuran (THF), and chloroform solutions as well as of the films of compounds 6–9 are shown in Figure 2a,b. The nonstructured low-energy bands at wavelengths of 350–450 nm are well seen in the absorption spectra of 6–9. The wavelengths of

• compound 8 had a slight impact on its red-shifted absorption spectra in comparison to that of other compounds (Figure 2a,b and Table 1). The photoluminescence spectra of toluene solutions of the compounds are characterized by non-structured shapes typical for ICT emissions (Figure 2c and Figure S1 in

• mCP are attributed to ICT bands of 6–9 (see Figure S3b in Supporting Information File 1). The temperature dependencies of PL spectra and PL decay curves of the 10 wt % molecular dispersions of compounds 6–9 in mCP are plotted in Figure 4a,b and Figures S4 and S5 in Supporting Information File 1. The

Controlling the reactivity of La@C₈₂ by reduction: reaction of the La@C₈₂ anion with alkyl halide with high regioselectivity

• Yutaka Maeda,
• Saeka Akita,
• Mitsuaki Suzuki,
• Michio Yamada,
• Takeshi Akasaka,
• Kaoru Kobayashi and
• Shigeru Nagase

Beilstein J. Org. Chem. 2023, 19, 1858–1866, doi:10.3762/bjoc.19.138

• @C2v-C82 anion with 1a. 110 °C, 2 h. (b) La@C2v-C82 with 1a. 110 °C, 2 h. (c) La@C2v-C82 anion with 1a. hv > 350 nm, 1 h. (d) La@C2v-C82 with 1a. hv > 350 nm, 1 h. Black line is the HPLC profiles of La@C2V-C82 at the same concentration as the reaction. Reaction mixtures with La@C2v-C82 anions were

• crystal has two independent units of 3a and three CS2 molecules as guest solvents. The difference between the two independent units is the direction of the tolyl group in the crystal (Supporting Information File 1, Figure S7). (a) Charge density of La@C2v-C82 anion as a function of its POAV values and (b

Thienothiophene-based organic light-emitting diode: synthesis, photophysical properties and application

• Recep Isci and
• Turan Ozturk

Beilstein J. Org. Chem. 2023, 19, 1849–1857, doi:10.3762/bjoc.19.137

• triphenylamine as donor and dimesitylboron as acceptor linked through a thieno[3,2-b]thiophene (TT) π-conjugated linker bearing a 4-MeOPh group, was designed, synthesized, and fabricated as an emitter via a solution process for an organic light-emitting diode (OLED) application. DMB-TT-TPA (8) exhibited

• layers are composed of various aromatic π-conjugated small molecules/polymers including thiophene, anthracene, carbazole, and triphenylamine [9][10][11][12][13]. Thienothiophenes are two annulated thiophene rings having four isomers, among which the most widely used isomer is thieno[3,2-b]thiophene (TT

• (excitation at λmax), respectively, leading to a mega Stokes shift (>100 nm) of 109 nm, which could be explained to be due to a fast relaxation from the excited state to the ground state as a result of a powerful intramolecular energy transfer between the TPA and boron groups through the thieno[3,2-b

N-Boc-α-diazo glutarimide as efficient reagent for assembling N-heterocycle-glutarimide diads via Rh(II)-catalyzed N–H insertion reaction

• Grigory Kantin,
• Pavel Golubev,
• Alexander Sapegin,
• Alexander Bunev and
• Dmitry Dar’in

Beilstein J. Org. Chem. 2023, 19, 1841–1848, doi:10.3762/bjoc.19.136

• α-bromo (α-oxysulfonyl) glutarimide (3, Scheme 1, route B). Although the first approach has readily available starting reagents, a simple synthesis process, and gives generally high yields, it is restricted in terms of the type of heterocycle that can be assembled (primarily cyclic imides and

• have been obtained. Glutarimide-based immunomodulatory drugs (IMiDs) and CRBN ligands. Examples of α-carbonyl NH-heterocycles for which N–H insertion products could not be obtained. Main literature approaches towards α-hetaryl glutarimides 1 (routes A and B) and new “diazo” methodology based on Rh(II

GlAIcomics: a deep neural network classifier for spectroscopy-augmented mass spectrometric glycans data

• Thomas Barillot,
• Baptiste Schindler,
• Baptiste Moge,
• Elisa Fadda,
• Franck Lépine and
• Isabelle Compagnon

Beilstein J. Org. Chem. 2023, 19, 1825–1831, doi:10.3762/bjoc.19.134

• ultimately be included in the algorithm for an optimal coverage of complex carbohydrates. (a) Fingerprint of an unknown monosaccharide. (b) Labelled reference spectra of monosaccharide standards. Typical experimental MS–IR spectra of the four categories of monosaccharides included in the first dataset. Blue

Recent advancements in iodide/phosphine-mediated photoredox radical reactions

• Tinglan Liu,
• Yu Zhou,
• Junhong Tang and
• Chengming Wang

Beilstein J. Org. Chem. 2023, 19, 1785–1803, doi:10.3762/bjoc.19.131

• radical and I· played a pivotal as an intermediate step in the production of alkyl iodides B. Compound B could undergo a further elimination reaction to yield various olefins 11. Regarding benzyl substrates, the radical I· demonstrated its efficacy as a reagent for hydrogen atom transfer (HAT

• facilitated by the process of photoexcited radical decarboxylation. On the other hand, the copper catalytic cycle involved the capture of alkyl radicals by the copper complex B, the activation of heteroatom-containing substrates 30 by a base-mediated proton transfer, and the subsequent reductive elimination

• -unsaturated phthalimide 33a. Simultaneously, radical III of the catalyst was also formed, accompanied by the extrusion of CO2. Subsequently, the alkyl radical A added to the carbon–carbon triple bond of enynal 32g, resulting in the formation of a vinyl radical intermediate B, followed by a 5-exo-trig

Active-metal template clipping synthesis of novel [2]rotaxanes

• Cătălin C. Anghel,
• Teodor A. Cucuiet,
• Niculina D. Hădade and
• Ion Grosu

Beilstein J. Org. Chem. 2023, 19, 1776–1784, doi:10.3762/bjoc.19.130

• , 29.2, 23.7 ppm; HRESI(+)-MS (m/z): [M + H]+ calcd for C140H171N10O15: 2233.2953; found, 2233.2883. a. Active-metal template (reported in the literature) and b. active-metal template clipping (used in this work) methods. Macrocyclic components of the [2]rotaxanes. Top: HRESI(+)-MS spectrum of the

Selectivity control towards CO versus H₂ for photo-driven CO₂ reduction with a novel Co(II) catalyst

• Lisa-Lou Gracia,
• Philip Henkel,
• Olaf Fuhr and
• Claudia Bizzarri

Beilstein J. Org. Chem. 2023, 19, 1766–1775, doi:10.3762/bjoc.19.129

• -centered d–d transitions. Cyclic voltammetry of complex 1 in 0.1 M TBAPF6 solution of (a) DMA and (b) DMA/TEOA 5:1 (v/v). Black curves are registered under Ar and red curves are recorded under CO2 atmosphere. A glassy-carbon disk was used as the working electrode and the internal references used are (a

• ) ferrocene and (b) decamethylferrocene. Scan rate was 100 mV s−1. Time evolution of CO (blue squares) and H2 (red triangles) with the power functional fitting (blue and red curve, respectively). Data were collected for photocatalytic tests in 5 mL DMA/TEA 7:1, [PS] = 0.5 mM; [1] = 0.025 mM; [BIH] = 10 mM

Charge carrier transport in perylene-based and pyrene-based columnar liquid crystals

• Alessandro L. Alves,
• Simone V. Bernardino,
• Carlos H. Stadtlober,
• Edivandro Girotto,
• Giliandro Farias,
• Rodney M. do Nascimento,
• Sergio F. Curcio,
• Thiago Cazati,
• Marta E. R. Dotto,
• Juliana Eccher,
• Leonardo N. Furini,
• Hugo Gallardo,
• Harald Bock and
• Ivan H. Bechtold

Beilstein J. Org. Chem. 2023, 19, 1755–1765, doi:10.3762/bjoc.19.128

• ) obtained is 23.7 Å for 1 and 22.9 Å for 2. The a/b aspect ratio of the Colrect phase of 2 is equal to 2.08, representing an elongation of around 20% concerning the hexagonal mesophase (where a/b = 1.73). The π-stacking distance between neighboring disks inside the columns, indicated by the (001) peak, is

• surface. Images of the complex geometries were obtained using the Chemcraft program (http://www.chemcraftprog.com). Raman spectra of 1 (a) and 2 (b) in powder. XRD measurements of 1 (a) and 2 (b) captured on cooling from the isotropic phase, indicating the Miller indices. Absorption and PL in chloroform

• solution and in spin-coated films for compounds 1 (a) and 2 (b). The PL was excited at the wavelength of maximum absorption. PL as a function of temperature for 1 (a) and 2 (b) casting films on heating. Left: PL spectra; right: intensity of the PL maximum. The PL was excited at the wavelength of maximum

Unprecedented synthesis of a 14-membered hexaazamacrocycle

• Anastasia A. Fesenko and
• Anatoly D. Shutalev

Beilstein J. Org. Chem. 2023, 19, 1728–1740, doi:10.3762/bjoc.19.126

• the most electrophilic C2 carbon of the pyrimidine ring in 8 to give intermediate A. Cleavage of the C2–N3 bond in the latter followed by proton transfer in the formed zwitterion B affords bis-amidrazone C. Next, two molecules of bis-amidrazone C react with each other forming adduct D, which either

• ); 13C NMR (150.90 MHz, DMSO-d6) δ 153.94 (С-2), 153.60 (С-6a), 147.48 (С-9b), 139.93 (С-5), 126.09 (С-9), 101.76 (С-9a), 40.39 (СH3); HRESIMS–TOF (m/z): [M + H]+ calcd for C7H7N6, 175.0727; found, 175.0733; Anal. calcd for C7H6N6: C, 48.27; H, 3.47; N, 48.25; found: C, 48.35; H, 3.52; N, 48.18. Method B

Effects of the aldehyde-derived ring substituent on the properties of two new bioinspired trimethoxybenzoylhydrazones: methyl vs nitro groups

• Dayanne Martins,
• Roberta Lamosa,
• Talis Uelisson da Silva,
• Carolina B. P. Ligiero,
• Sérgio de Paula Machado,
• Daphne S. Cukierman and
• Nicolás A. Rey

Beilstein J. Org. Chem. 2023, 19, 1713–1727, doi:10.3762/bjoc.19.125

• Dayanne Martins Roberta Lamosa Talis Uelisson da Silva Carolina B. P. Ligiero Sergio de Paula Machado Daphne S. Cukierman Nicolas A. Rey Departmento de Química, Pontifícia Universidade Católica do Rio de Janeiro (PUC-Rio), Rio de Janeiro, 22451-900, Brazil Instituto de Química, Universidade

• structure was calculated with the Pymol tool [66]. ORTEP representation of the new N-acylhydrazones synthesized in the present work, drawn with thermal ellipsoids at 30% probability. Left: hdz-CH3 and right: hdz-NO2. (A) Superposition of molecular structures and stacked motifs of (B) hdz-CH3 and (C) hdz-NO2

• . Overlap of the experimental (carbon atoms colored in gray) and theoretical structures (calculated with B3LYP/6-311G(d,p) in gas and water phases colored in yellow and cyan, respectively): hdz-CH3 seen from (A) above and (B) from the side; hdz-NO2 seen from (C) above and (D) from the side. The optimized