Quantifying the ability of the CF₂H group as a hydrogen bond donor

• Matthew E. Paolella,
• Daniel S. Honeycutt,
• Bradley M. Lipka,
• Jacob M. Goldberg and
• Fang Wang

Beilstein J. Org. Chem. 2025, 21, 189–199, doi:10.3762/bjoc.21.11

• interactions involving the CF2H group are underway. Examples of solid state structures exhibiting CF2H group-mediated hydrogen bond interactions [16][18][21]. Hydrogen bonding interactions involving the CF2H group are highlighted in orange. Hydrogen bond donors investigated in this study. For all cationic

Hydrogen-bonded macrocycle-mediated dimerization for orthogonal supramolecular polymerization

• Wentao Yu,
• Zhiyao Yang,
• Chengkan Yu,
• Xiaowei Li and
• Lihua Yuan

Beilstein J. Org. Chem. 2025, 21, 179–188, doi:10.3762/bjoc.21.10

• structure would also be found in the solid state. Fortunately, single crystals of the complex H1 ⊃ G1 were obtained by slow evaporation of chloroform/acetone solvent (1:1, v/v) into a small amount of methanol over the course of two weeks. Indeed, analysis of the crystal structure of the complex revealed a

Nickel-catalyzed cross-coupling of 2-fluorobenzofurans with arylboronic acids via aromatic C–F bond activation

• Takeshi Fujita,
• Haruna Yabuki,
• Ryutaro Morioka,
• Kohei Fuchibe and
• Junji Ichikawa

Beilstein J. Org. Chem. 2025, 21, 146–154, doi:10.3762/bjoc.21.8

• Takeshi Fujita Haruna Yabuki Ryutaro Morioka Kohei Fuchibe Junji Ichikawa The Institute for Solid State Physics, The University of Tokyo, 5-1-5 Kashiwanoha, Kashiwa, Chiba 277-8581, Japan Division of Chemistry, Faculty of Pure and Applied Sciences, University of Tsukuba, 1-1-1 Tennodai, Tsukuba

• the Institute for Solid State Physics, the University of Tokyo (1H, 13C, and 19F NMR spectrometer, mass spectroscopy system, and IR spectroscopy system in Mori Laboratory). Funding This work was financially supported by JSPS KAKENHI Grant Number JP21K05066 in Grant-in-Aid for Scientific Research (C

Efficient synthesis of fluorinated triphenylenes with enhanced arene–perfluoroarene interactions in columnar mesophases

• Yang Chen,
• Jiao He,
• Hang Lin,
• Hai-Feng Wang,
• Ping Hu,
• Bi-Qin Wang,
• Ke-Qing Zhao and
• Bertrand Donnio

Beilstein J. Org. Chem. 2024, 20, 3263–3273, doi:10.3762/bjoc.20.270

• electronic structures of the triphenylenes, and their supramolecular arene–perfluoroarene slipped stacks (J-aggregate) result in G66 with orange-yellow color fluorescence in the solid state. Fluorotriphenylene derivatives and their nonfluorinated homologs obtained by SNFAr from 2,2'-dilithio-4,4',5,5

• concentration of 1 × 10−5 mol/L and in solid-state thin film. DFT calculated frontier molecular orbitals and optimized molecular structures for F1 and G11. Synthesis, yields, and nomenclature of 1,2,4-trifluoro-6,7,10,11-tetraalkoxy-3-(perfluorophenyl)triphenylene (Fn, n = 3–12) and corresponding 1,1',3,3',4,4

Synthesis of extended fluorinated tripeptides based on the tetrahydropyridazine scaffold

• Thierry Milcent,
• Pascal Retailleau,
• Benoit Crousse and
• Sandrine Ongeri

Beilstein J. Org. Chem. 2024, 20, 3174–3181, doi:10.3762/bjoc.20.262

• intramolecular Michael addition. Preliminary conformational studies on tripeptides including this scaffold in the central position show an extended conformation in solution (NMR) and in the solid state (X-ray). Keywords: fluoroalkyl groups; heterocycles; hydrazino acids; peptides; tetrahydropyridazines

Controlled oligomerization of [1.1.1]propellane through radical polarity matching: selective synthesis of SF₅- and CF₃SF₄-containing [2]staffanes

• Jón Atiba Buldt,
• Wang-Yeuk Kong,
• Yannick Kraemer,
• Masiel M. Belsuzarri,
• Ansh Hiten Patel,
• James C. Fettinger,
• Dean J. Tantillo and
• Cody Ross Pitts

Beilstein J. Org. Chem. 2024, 20, 3134–3143, doi:10.3762/bjoc.20.259

• -containing [2]staffane in the solid state. Keywords: pentafluorosulfanylation; [1.1.1]propellane; radical chain oligomerization; staffanes; strain-release; Introduction In various radical additions of X–Y across [1.1.1]propellane (1), functionalized oligomers known as [n]staffanes – with n > 1, where n

Tunable full-color dual-state (solution and solid) emission of push–pull molecules containing the 1-pyrindane moiety

• Anastasia I. Ershova,
• Sergey V. Fedoseev,
• Konstantin V. Lipin,
• Mikhail Yu. Ievlev,
• Oleg E. Nasakin and
• Oleg V. Ershov

Beilstein J. Org. Chem. 2024, 20, 3016–3025, doi:10.3762/bjoc.20.251

• solid state). Emission maxima ranged from 469 to 721 nm in solution depending on the solvent and type of donor substituent, and from 493 to 767 nm in the solid state. For the arylidene derivative of pyrindane with a dimethylamino group, it was shown that fluorescence can be changed by the action of an

• acid both in solution and in the solid state. Keywords: dual-state emission; full-color emission; nitriles; push–pull molecules; pyrindane; stilbazole; Introduction Over the past decades, heteroaromatic push–pull molecules have attracted great attention due to their widespread use in materials

• able to emit in two different states (solution and solid state). This makes them more versatile and allows them to be used for the creation of fluorescent materials with different characteristics. Molecules exhibiting DSE are required to have certain structural features. First, they often contain donor

Tailored charge-neutral self-assembled L₂Zn₂ container for taming oxalate

• David Ocklenburg and
• David Van Craen

Beilstein J. Org. Chem. 2024, 20, 3007–3015, doi:10.3762/bjoc.20.250

• sufficient quality to obtain a solid-state structure of the oxalate host–guest complex [(C2)@L2Zn2]2− so that we utilized DFT calculations to model the expected structure of the host–guest species (Figure 3a). Therefore, we funneled structural information obtained from NMR spectra into our starting geometry

The charge transport properties of dicyanomethylene-functionalised violanthrone derivatives

• Sondos A. J. Almahmoud,
• Joseph Cameron,
• Dylan Wilkinson,
• Michele Cariello,
• Claire Wilson,
• Alan A. Wiles,
• Peter J. Skabara and
• Graeme Cooke

Beilstein J. Org. Chem. 2024, 20, 2921–2930, doi:10.3762/bjoc.20.244

• one with branched alkyl chains, 3a. This could be the result of the more highly disordered packing arrangement of this molecule in the solid state, induced by the branched side chains that hinder the formation of π–π stacking interactions. The influence of dicyanomethylene groups on the charge

• pass through the device [30]. The π–π intermolecular interactions, the molecular stacking and mobility of a solution-processable violanthrone derivative has been studied. It was shown that π–π stacking can be enhanced in solution and in the solid state by adding a non-solvent (n-hexane) to chloroform

• linear side chains in compounds 3b and 3c, might favour intermolecular π–π interactions and crystallinity in the solid state, therefore providing an easier pathway for charge carriers to hop from one molecule to nearby molecules. The introduction of the bulky dicyanomethylene groups in 3b resulted in a

Recent advances in transition-metal-free arylation reactions involving hypervalent iodine salts

• Ritu Mamgain,
• Kokila Sakthivel and
• Fateh V. Singh

Beilstein J. Org. Chem. 2024, 20, 2891–2920, doi:10.3762/bjoc.20.243

• capability to function as radical initiators. The use of diaryliodonium salts as efficient electrophilic arylating reagents in a wide range of organic transformations is due to their unique features such as solid-state nature, excellent stability, and the presence of a robust leaving group [39][40][41][42

Photoluminescence color-tuning with polymer-dispersed fluorescent films containing two fluorinated diphenylacetylene-type fluorophores

• Kazuki Kobayashi,
• Shigeyuki Yamada,
• Motohiro Yasui and
• Tsutomu Konno

Beilstein J. Org. Chem. 2024, 20, 2682–2690, doi:10.3762/bjoc.20.225

• electroluminescent devices have attracted significant attention as lightweight and energy-saving optical devices, and there has been a strong demand for the development of luminescent materials. Until now, the design of solid-state light-emitting materials has not been established, and therefore, their development

• has been severely delayed [4][5][6]. However, since Tang et al. first reported the aggregation-induced emission phenomenon in 2001 [7], the development of solid-state light-emitting materials has accelerated significantly [8][9][10]. Many photoluminescent materials that emit blue, green, and yellow

• as electron-donating groups was shown to promote intramolecular charge transfer (ICT) and shifted the PL wavelength to longer wavelengths, resulting in yellow or orange fluorescence in the solid state [21][22]. In addition, cross-linking between the amino group and attached benzene ring effectively

Anion-dependent ion-pairing assemblies of triazatriangulenium cation that interferes with stacking structures

• Yohei Haketa,
• Takuma Matsuda and
• Hiromitsu Maeda

Beilstein J. Org. Chem. 2024, 20, 2567–2576, doi:10.3762/bjoc.20.215

• synthesized to investigate the interactions for the bulky cation. Single-crystal X-ray analysis of the TATA+ ion pairs revealed solid-state ion-pairing assemblies without stacking at the cationic π-planes. The TATA+ cation showed counteranion-dependent assembly structures, with smaller counteranions located

• at the top of TATA+ and bulkier counteranions displaced from the TATA+ plane to interact with the surrounding TATA+. Keywords: charged π-electronic systems; ion pairs; single-crystal X-ray analysis; solid-state assemblies; triazatriangulenium cation; Introduction Triangulenium cations [1][2] have

• modifications of the N-aryl units as sterically hindered substituents significantly affect the assembling behaviors, their solid-state packing structures are largely unknown. In this study, ion pairs (salts) of an N-aryl-substituted TATA+ as a bulky cation with various counteranions were prepared for

Synthesis and conformational analysis of pyran inter-halide analogues of ᴅ-talose

• Olivier Lessard,
• Mathilde Grosset-Magagne,
• Paul A. Johnson and
• Denis Giguère

Beilstein J. Org. Chem. 2024, 20, 2442–2454, doi:10.3762/bjoc.20.208

• halo-divergent strategy from known 1,6-anhydro-2,3-dideoxy-2,3-difluoro-β-ᴅ-mannopyranose. In solution and in the solid-state, all analogues adopt standard 4C1-like conformations despite 1,3-diaxial repulsion between the F2 and the C4 halogen. Moreover, the solid-state conformational analysis of

• orbitals. Keywords: organofluorine; pyran inter-halide; solid-state conformation; solution-state conformation; Introduction Polyfluorinated pyran analogues of carbohydrates have attracted attention over the years. This class of glycomimetics has great biological potential with useful applications [1][2

• ) [24]. The solution and the solid-state conformational analysis were supplemented with DFT calculations to understand key conformational drivers. This study adds more data to the field of nuclear magnetic resonance (NMR) spectroscopy of polyhalogenated molecules. It should be noted that the NMR

Evaluating the halogen bonding strength of a iodoloisoxazolium(III) salt

• Dominik L. Reinhard,
• Anna Schmidt,
• Marc Sons,
• Julian Wolf,
• Elric Engelage and
• Stefan M. Huber

Beilstein J. Org. Chem. 2024, 20, 2401–2407, doi:10.3762/bjoc.20.204

• donors in recent years. Herein, a new structural motif for this compound class was developed: iodoloisoxazolium salts, bearing a cyclic five-membered iodolium core fused with an isoxazole ring. A derivative of this class was synthesized and investigated in the solid state by X-ray crystallography

Synthesis and reactivity of the di(9-anthryl)methyl radical

• Tomohiko Nishiuchi,
• Kazuma Takahashi,
• Yuta Makihara and
• Takashi Kubo

Beilstein J. Org. Chem. 2024, 20, 2254–2260, doi:10.3762/bjoc.20.193

• unit allows for spin localization at the 10-position of anthracene through C–C bond rotation, resulting in a tail-to-tail σ-dimer (Figure 1b). The σ-dimer exhibits an equilibrium state between the monomer radical and the σ-dimer in solution, and mechano-stimulus-induced C–C bond fission in the solid

• state yields the monomer radical [16][17][18]. Therefore, aromatic hydrocarbon radicals with Ant units possess both stability and reactivity depending on the conditions, giving them high potential for use as reactive catalysts [22][23] and stimuli-responsive sensors [24][25]. To further investigate this

Multicomponent syntheses of pyrazoles via (3 + 2)-cyclocondensation and (3 + 2)-cycloaddition key steps

• Ignaz Betcke,
• Alissa C. Götzinger,
• Maryna M. Kornet and
• Thomas J. J. Müller

Beilstein J. Org. Chem. 2024, 20, 2024–2077, doi:10.3762/bjoc.20.178

• solvents (DES) [83]. Catalysis can also be achieved using molecular iodine [84], AlCl3 [85], sodium ascorbate [86], and even solid-state and nanoparticle-mediated catalysts like CuO/ZrO2 [87], Fe3O4@Si@MoO2 [88], caspacin-cyclodextrin functionalized magnetite nanoparticles (CPS CD) [89], and Mg-Fe

• solution and in the solid state [127]. Furthermore, even sugar-functionalized pyrazoles have been accessed by this approach [128], and it was readily implemented in a continuous flow reactor [129]. Besides traditional Sonogashira catalyst systems, highly reactive and reusable immobilized Pd-complexes, such

The Groebke–Blackburn–Bienaymé reaction in its maturity: innovation and improvements since its 21st birthday (2019–2023)

• Cristina Martini,
• Muhammad Idham Darussalam Mardjan and
• Andrea Basso

Beilstein J. Org. Chem. 2024, 20, 1839–1879, doi:10.3762/bjoc.20.162

Oxidative fluorination with Selectfluor: A convenient procedure for preparing hypervalent iodine(V) fluorides

• Samuel M. G. Dearman,
• Xiang Li,
• Yang Li,
• Kuldip Singh and
• Alison M. Stuart

Beilstein J. Org. Chem. 2024, 20, 1785–1793, doi:10.3762/bjoc.20.157

• (1–3 % spectroscopic yield) when BF3·OEt2 was added to the reaction mixture. X-ray crystallography and DFT calculations The solid-state structure of difluoroiodane 6 is shown in Figure 2 and displays the expected square pyramidal geometry around the iodine atom, with only minor distortion (τ5 = 0.191

• with the solid state structures. As expected, the calculated atomic charge on iodine was much higher for the iodine(V) fluorides (1.689–1.766) than in the iodine(III) fluorides (0.957–1.009) resulting in shorter I–F and I–O bond lengths. Interestingly, there is a slightly lower charge on iodine in

• iodine(V) fluorides in good yields (72–90%). Unfortunately, none of the iodine(V) fluorides reacted with phenylmagnesium bromide to form fluorobenzene and we were never able to repeat Amey and Martin’s fluorination of phenylmagnesium bromide. A solid-state structure of 6 and DFT calculations on 6 and 20

Synthesis and characterization of 1,2,3,4-naphthalene and anthracene diimides

• Adam D. Bass,
• Daniela Castellanos,
• Xavier A. Calicdan and
• Dennis D. Cao

Beilstein J. Org. Chem. 2024, 20, 1767–1772, doi:10.3762/bjoc.20.155

• cyclic imides. The solid-state structures of the N-phenyl derivatives, determined by X-ray crystallography, reveal changes in packing preference based on the number of aromatic rings in the core. The optical and electronic properties of the title compounds compare favorably with other previously

Competing electrophilic substitution and oxidative polymerization of arylamines with selenium dioxide

• Vishnu Selladurai and
• Selvakumar Karuthapandi

Beilstein J. Org. Chem. 2024, 20, 1221–1235, doi:10.3762/bjoc.20.105

• due to N–H stretching of the polymer [43][44]. The peak appearing at around 3000 cm−1 corresponded to the aryl C–H stretching. The peaks observed at 1593 and 1479 cm−1 were associated with C=C and C=N stretching, respectively. The obtained result was further supported by solid-state synthesis of

• structure, it self-organized through π–π interaction between the oxamide motif and the aryl π-framework. Further, the CH…O=C interaction facilitated the formation of ladder-like packing in the solid state (Figure S36, Supporting Information File 1). The molecular structure of oxamide 13 is shown in Figure 3

Kinetically stabilized 1,3-diarylisobenzofurans and the possibility of preparing large, persistent isoacenofurans with unusually small HOMO–LUMO gaps

• Qian Liu and
• Glen P. Miller

Beilstein J. Org. Chem. 2024, 20, 1099–1110, doi:10.3762/bjoc.20.97

• stabilized hexacenes. Their beautiful work documented the lack of stability associated with isoanthracenofurans. Thus, their 1,3-diarylisoanthracenofurans rapidly oxidized in solution to form endoperoxides [3]. These compounds persisted longer in the solid state, but clearly the lack of stability and

• ’,4’,6’-triethylphenyl substituents in compounds 3 and 23, respectively, provides for enhanced steric congestion at the most reactive 1,3-carbons of the furan ring. Likewise, 3 and 23 are stable indefinitely in the solid state and persist for days in solution phase without significant decomposition

Structure–property relationships in dicyanopyrazinoquinoxalines and their hydrogen-bonding-capable dihydropyrazinoquinoxalinedione derivatives

• Tural N. Akhmedov,
• Ajeet Kumar,
• Daken J. Starkenburg,
• Kyle J. Chesney,
• Khalil A. Abboud,
• Novruz G. Akhmedov,
• Jiangeng Xue and
• Ronald K. Castellano

Beilstein J. Org. Chem. 2024, 20, 1037–1052, doi:10.3762/bjoc.20.92

• ). Single crystal X-ray diffraction data could be obtained for three DPQDs. One reveals pairwise hydrogen bonding in the solid state as well as a herringbone packing arrangement rendering it a promising candidate for additional studies in the context of organic optoelectronic devices. Keywords: conjugated

• molecular ordering in solid-state organic semiconductors, thereby dictating charge transport pathways as well as carrier mobilities of both electrons and holes [4][5][6]. Furthermore, strong hydrogen bonding interactions effectively modulate energy levels of semiconducting materials, affecting the bandgap

• exhibits a noteworthy impact on the thermal stabilities (analyzed by TGA) of the compounds. The single-crystal X-ray diffraction of DPQD 2b exhibits a desirable herringbone solid-state arrangement for a potential OFET application. Complementary gas-phase computational analysis has provided insight into the

Skeletal rearrangement of 6,8-dioxabicyclo[3.2.1]octan-4-ols promoted by thionyl chloride or Appel conditions

• Martyn Jevric,
• Julian Klepp,
• Johannes Puschnig,
• Oscar Lamb,
• Christopher J. Sumby and
• Ben W. Greatrex

Beilstein J. Org. Chem. 2024, 20, 823–829, doi:10.3762/bjoc.20.74

• open chain aldehydes present in solution (≈5%) with a doublet at δ 9.6 ppm, with the configuration of the hemiacetal centre confirmed in the solid state by X-ray crystallography on 12a and 12d. The 1H and 13C NMR spectra for 13b,d,e were similar to the starting materials, except that the resonances

Regioselective quinazoline C2 modifications through the azide–tetrazole tautomeric equilibrium

• Dāgs Dāvis Līpiņš,
• Andris Jeminejs,
• Una Ušacka,
• Anatoly Mishnev,
• Māris Turks and
• Irina Novosjolova

Beilstein J. Org. Chem. 2024, 20, 675–683, doi:10.3762/bjoc.20.61

• explanation for the present tetrazole form in the solutions. Surprisingly, FTIR and X-ray analyses of 12a in the solid state indicated the existence of 12a in the azide form. In subsequent experiments it was discovered that for less nucleophilic N-nucleophiles (piperidine, morpholine, N-methylpiperazine) C2

Switchable molecular tweezers: design and applications

• Pablo Msellem,
• Maksym Dekthiarenko,
• Nihal Hadj Seyd and
• Guillaume Vives

Beilstein J. Org. Chem. 2024, 20, 504–539, doi:10.3762/bjoc.20.45

• tweezers with tert-butyl groups positioned farther from the salphen via alkyne spacers were synthesized [42]. While, like in the parent tweezers 12, no intercalation of aromatic guests was observed in the closed form, strong intramolecular and intermolecular Pt–Pt bonds were achieved in the solid state