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

• Tetrathiafulvalene (TTF, Figure 1) is a redox-active molecule that has been widely explored in materials chemistry and supramolecular chemistry [1][2][3][4][5][6][7][8]. TTF reversibly undergoes two sequential one-electron oxidations, generating first a radical cation (TTF+•) and subsequently a dication (TTF2

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

• there might be more to win before the electrons jump. Being general and easy to use, the introduced supramolecular organocatalytic systems promise to lift all involved topics to a new level of significance. Essentially every reaction consists of the movement of electrons, from nucleophile to

Substituent-controlled construction of A₄B₂-hexaphyrins and A₃B-porphyrins: a mechanistic evaluation

• Seda Cinar,
• Dilek Isik Tasgin and
• Canan Unaleroglu

Beilstein J. Org. Chem. 2023, 19, 1832–1840, doi:10.3762/bjoc.19.135

• of porphyrinogen and hexaphyrinogen forms. Keywords: A4B2-hexaphyrin; A3B-porphyrin; N-tosylimine; Cu(OTf)2 catalysis; HRESI–TOF analysis; Introduction Porphyrins and expanded porphyrins have found widespread applications in supramolecular chemistry [1][2][3][4]. Expanded porphyrins are utilized as

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

• Catalin C. Anghel Teodor A. Cucuiet Niculina D. Hadade Ion Grosu Babeș-Bolyai University, Faculty of Chemistry and Chemical Engineering, Supramolecular Organic and Organometallic Chemistry Centre, 11 Arany Janos Str., RO-400028-Cluj-Napoca, Romania University of Bucharest, Faculty of Chemistry

• ; Department of Organic Chemistry, Biochemistry and Catalysis, Research Centre of Applied Organic Chemistry, 90-92 Panduri Street, RO-050663 Bucharest, Romania 10.3762/bjoc.19.130 Abstract Mechanically interlocked molecules (MIMs) have been important synthetic targets in supramolecular chemistry due to their

• in 2016. While initially obtained as chemical curiosities, rotaxanes offer now exciting opportunities for scientific advancements in supramolecular chemistry and applications in various fields ranging from molecular machines and switches [4][5][6][7][8][9] to catalysis [10][11], molecular electronics

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

• ), organic light-emitting diodes (OLEDs) and sensors [1][2]. Columnar liquid crystals are attractive due to their solution processability and their self-organization in highly anisotropic supramolecular architectures, which favors the mainly one-dimensional migration of charge carriers with an anisotropy of

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

• around the conjugated amide single bond (N–C=O). N-Acylhydrazones have also gained attention in literature due to other applications, ranging from medicine to supramolecular chemistry [7][8]. Among their applicability is the area of optoelectronic devices, in which they are used for the manufacture of

• supramolecular organization of the N-acylhydrazones was also studied through their Hirshfeld surfaces, in which π–π interactions play an important role. When the normalized distance between a molecule and the closest neighbors are plotted (Figures S2A and S2C, and S3A and S3C in Supporting Information File 1

Tying a knot between crown ethers and porphyrins

• Maksym Matviyishyn and
• Bartosz Szyszko

Beilstein J. Org. Chem. 2023, 19, 1630–1650, doi:10.3762/bjoc.19.120

• the possible future directions. Keywords: crown ethers; porphyrinoids; self-assembly; sensors; supramolecular chemistry; Introduction Many areas of modern supramolecular chemistry, organic, inorganic, materials and coordination chemistry, are based upon macrocyclic compounds of specifically-designed

• structures and tailored functions [1][2][3]. The design of novel macrocyclic compounds has laid the ground for phenomenal developments constituting supramolecular chemistry as a branch of chemical sciences. These fundamental developments included the discovery of crown ethers by Pedersen [4], followed by the

• porphyrins as multitopic receptors, sensors, and supramolecular hosts, with applications in ion transport, catalysis, and polymeric materials [22][40][41][42][43][44][45]. In 1984 Lehn, Sessler and co-workers developed double-side-strapped crowned porphyrins, which served as tritopic and tetratopic receptors

Complexes of resorcin[4]arene with secondary amines: synthesis, solvent influence on “in-out” structure, and theoretical calculations of non-covalent interactions

• Waldemar Iwanek

Beilstein J. Org. Chem. 2023, 19, 1525–1536, doi:10.3762/bjoc.19.109

• exchange and dispersion interactions in CHCl3 in relation to DMSO are the driving forces behind the placement of sec-amine molecules into the R[4]A cavity and the formation of “in” type complexes. Keywords: complexes; DFT calculations; hydrogen bond; resorcin[4]arene; supramolecular chemistry

• role in their self-association and the formation of larger supramolecular structures such as dimers [3], hexamers [4][5], octamers [6], and nano-aggregates [7]. The stability of these structures is highly reliant on the type of solvent used. Most of the works are studies of non-polar environments such

• ], amino alcohols [10], and amino acids [11] have been studied due to their potential applications in supramolecular chemistry, drug delivery, and molecular recognition. The complexation of R[4]A with amines is based on the formation of hydrogen bonds between the hydroxy groups of the resorcinol units and

One-pot nucleophilic substitution–double click reactions of biazides leading to functionalized bis(1,2,3-triazole) derivatives

• Hans-Ulrich Reissig and
• Fei Yu

Beilstein J. Org. Chem. 2023, 19, 1399–1407, doi:10.3762/bjoc.19.101

• discovery of the copper-catalyzed alkyne azide (3 + 2) cycloaddition (CuAAC) [3][4], has dramatically changed the approaches to many problems in chemistry, supramolecular chemistry, materials science, biological chemistry and related fields (selected reviews: [5][6][7][8][9][10][11][12][13][14][15

Synthesis of ether lipids: natural compounds and analogues

• Marco Antônio G. B. Gomes,
• Alicia Bauduin,
• Chloé Le Roux,
• Romain Fouinneteau,
• Wilfried Berthe,
• Mathieu Berchel,
• Hélène Couthon and
• Paul-Alain Jaffrès

Beilstein J. Org. Chem. 2023, 19, 1299–1369, doi:10.3762/bjoc.19.96

• with biomembranes via supramolecular interactions with the lipids and proteins that are embedded in these membranes. We can hypothesis that their mechanism of action occurs via a direct interaction with membrane proteins or by a modification of the biophysical properties of the membranes. It must be

Exploring the role of halogen bonding in iodonium ylides: insights into unexpected reactivity and reaction control

• Carlee A. Montgomery and
• Graham K. Murphy

Beilstein J. Org. Chem. 2023, 19, 1171–1190, doi:10.3762/bjoc.19.86

• numerous similar attributes, halogen bonding has also proven to be a viable alternative in methodologies that rely on hydrogen bond initiation. For example, both halogen- and hydrogen bonding can be used in supramolecular chemistry as the binding mechanism in photoresponsive receptors [73][74][75][76][77

Cyclodextrins as building blocks for new materials

• Miriana Kfoury and
• Sophie Fourmentin

Beilstein J. Org. Chem. 2023, 19, 889–891, doi:10.3762/bjoc.19.66

• . CDs are the most studied supramolecular hosts. They provide the most extensive database on molecular recognition in the literature, with more than 100,000 publications [2]. CDs owe their success not only to the unique molecular structure [3], which allows them to act as host compounds, but also to

• , and catalysis [2][5][12]. Molecular encapsulation is not the only application area for these macrocyclic components at present. CDs are versatile molecules. Their 3D structure makes them exceptional building blocks for the design of innovative supramolecular architectures due to the differential

• science that require high performance with minimal environmental impact. They are involved in the construction of interlocked molecules (rotaxanes and catenanes), supramolecular polymers, artificial enzymes, hydrogels, metal–organic frameworks, supramolecular solvents, fibers, nanotubes, nanoparticles

Light-responsive rotaxane-based materials: inducing motion in the solid state

• Adrian Saura-Sanmartin

Beilstein J. Org. Chem. 2023, 19, 873–880, doi:10.3762/bjoc.19.64

• pseudorotaxanes, the supramolecular interactions between the counterparts are retained, thus constituting stable intertwined species showing analogous properties to those of rotaxanes. The pseudorotaxanes 1 were constituted by a dibenzo-24-crown-8 cyclic component and an ammonium-based thread functionalized with

• supramolecular gels (Figure 2a) [52]. Upon irradiation using a UV-light-emitting diode (LED) and a visible LED as sources, the reversible cleavage of the trithiocarbonate stoppers was accomplished, thus allowing the dethreading [53] of the wheels to take place by the shuttling of the macrocycles along the thread

A fluorescent probe for detection of Hg²⁺ ions constructed by tetramethyl cucurbit[6]uril and 1,2-bis(4-pyridyl)ethene

• Xiaoqian Chen,
• Naqin Yang,
• Yue Ma,
• Xinan Yang and
• Peihua Ma

Beilstein J. Org. Chem. 2023, 19, 864–872, doi:10.3762/bjoc.19.63

• Xiaoqian Chen Naqin Yang Yue Ma Xinan Yang Peihua Ma Key Laboratory of Macrocyclic and Supramolecular Chemistry of Guizhou Province, Guizhou University, Guiyang 550025, China Guiyang College of Humanities and Science, Guiyang 550025, China 10.3762/bjoc.19.63 Abstract In this paper, tetramethyl

• cucurbit[6]uril (TMeQ[6]) and 1,2-bis(4-pyridyl)ethene (G) were used to construct a supramolecular fluorescent probe G@TMeQ[6]. The host–guest interaction between TMeQ[6] and G was investigated using 1H NMR spectroscopy, single-crystal X-ray diffraction and various experimental techniques. The results show

• form various host–guest inclusion complexes [16][17][18][19][20], which have broad application prospects in supramolecular catalysis [21][22][23], molecular recognition [24][25], and drug delivery [26][27]. In recent years, in the field of supramolecular chemistry, the detection of analytes based on

pH-Responsive fluorescent supramolecular nanoparticles based on tetraphenylethylene-labelled chitosan and a six-fold carboxylated tribenzotriquinacene

• Nan Yang,
• Yi-Yan Zhu,
• Wei-Xiu Lin,
• Yi-Long Lu and
• Wen-Rong Xu

Beilstein J. Org. Chem. 2023, 19, 635–645, doi:10.3762/bjoc.19.45

• in the presence of TBTQ-C6 was greatly improved. In addition, the fluorescence of CS-TPE was significantly enhanced by introducing TBTQ-C6, and remained relatively stable with variations in pH for both CS-TPE and TBTQ-C6/CS-TPE. Such pH-responsive supramolecular spherical nanoparticles with stable

• extensive attention owing to their potential applications in biomedicine, chemical sensing and as catalysts [1][2]. It is possible to regulate the formation and breakdown of supramolecular structures using external stimuli, such as pH, light, temperature, enzymes, and competing reagents [3][4]. Among these

• stimuli, pH response is of particular interest in the construction of supramolecular systems for intelligent drug delivery because of the presence of pH gradients in the microenvironment of organs, tissues, and cell organelles [5]. In the past years, pH-responsive and other stimuli-responsive

Phenanthridine–pyrene conjugates as fluorescent probes for DNA/RNA and an inactive mutant of dipeptidyl peptidase enzyme

• Josipa Matić,
• Tana Tandarić,
• Marijana Radić Stojković,
• Filip Šupljika,
• Zrinka Karačić,
• Ana Tomašić Paić,
• Lucija Horvat,
• Robert Vianello and
• Lidija-Marija Tumir

Beilstein J. Org. Chem. 2023, 19, 550–565, doi:10.3762/bjoc.19.40

• ]. Excimers are formed when pyrene moieties form supramolecular complexes by intermolecular or intramolecular π–π interactions, causing a significant shift of single pyrene bands to longer wavelengths. Pyrenes are often used as a sensor part of receptor molecules, so their excimer bands switch on/off to

• applications [9]. These compounds have a very large aromatic surface suitable to form self-assembled supramolecular structures by intermolecular π–π interactions and showed excimer fluorescence in thin film and in the solid state. Kawai et al. reported exciplex formation between pyrene and guanine in polar

Discrimination of β-cyclodextrin/hazelnut (Corylus avellana L.) oil/flavonoid glycoside and flavonolignan ternary complexes by Fourier-transform infrared spectroscopy coupled with principal component analysis

• Nicoleta G. Hădărugă,
• Gabriela Popescu,
• Dina Gligor (Pane),
• Cristina L. Mitroi,
• Sorin M. Stanciu and
• Daniel Ioan Hădărugă

Beilstein J. Org. Chem. 2023, 19, 380–398, doi:10.3762/bjoc.19.30

• cheap method for the evaluation of quality and similarity/characteristics of these new types of cyclodextrin-based ternary complexes having enhanced properties and stability. Keywords: antioxidant; cyclodextrin; flavonoid; hazelnut vegetable oil; ternary supramolecular inclusion complex; Introduction

• compounds [5]. The resulting supramolecular inclusion complexes provide enhanced water solubility and bioavailability/bioaccessibility of the nanoencapsulated bioactive compounds, higher oxidative and thermal stability or photostability of labile compounds, and their controlled release [6][7]. Vegetable oil

• FA moieties interact with the β-CD host molecules. This was the reason to use such non-equimolar ratios. If a theoretical 3:1 interaction can be considered, the formation of such β-CD/triglyceride supramolecular system in practice is limited by the steric hindrance. On the other hand, ternary

CuAAC-inspired synthesis of 1,2,3-triazole-bridged porphyrin conjugates: an overview

• Dileep Kumar Singh

Beilstein J. Org. Chem. 2023, 19, 349–379, doi:10.3762/bjoc.19.29

• suggested a weak intramolecular inter-porphyrin communication. Further investigation also revealed that the interaction of the star compound 129 with DABCO and Bipy possibly led to the double star formed by the axial coordination of ligand with zinc centers. The synthesis of supramolecular nanoassemblies

• )porphyrin 130a,b and 6-deoxy-6-azido-PM-β-CD 124 using copper sulfate and sodium ascorbate in THF/H2O (Scheme 26). Furthermore, the supramolecular nanoarchitectures as potential candidates for controlling drug delivery were prepared by complexing the porphyrins 131a,b with tetrasodium

• porphyrin 174 and stirred at room temperature for 24 h, solubilization occurred, resulting in a homogeneous solution. This is due to the formation of a supramolecular assembly in which the hydrophobic adamantane arms of 176b are sequestered by the β-CD arms of porphyrin 174, resulting in water solubility

Inclusion complexes of the steroid hormones 17β-estradiol and progesterone with β- and γ-cyclodextrin hosts: syntheses, X-ray structures, thermal analyses and API solubility enhancements

• Alexios I. Vicatos,
• Zakiena Hoossen and
• Mino R. Caira

Beilstein J. Org. Chem. 2022, 18, 1749–1762, doi:10.3762/bjoc.18.184

• Alexios I. Vicatos Zakiena Hoossen Mino R. Caira Centre for Supramolecular Chemistry Research (CSCR), Department of Chemistry, University of Cape Town, Rondebosch 7701, South Africa 10.3762/bjoc.18.184 Abstract Overcoming the challenges of poor aqueous solubility of active pharmaceutical

Preparation of β-cyclodextrin-based dimers with selectively methylated rims and their use for solubilization of tetracene

• Konstantin Lebedinskiy,
• Volodymyr Lobaz and
• Jindřich Jindřich

Beilstein J. Org. Chem. 2022, 18, 1596–1606, doi:10.3762/bjoc.18.170

• Konstantin Lebedinskiy Volodymyr Lobaz Jindrich Jindrich Department of Organic Chemistry, Faculty of Science, Charles University, Hlavova 8, 128 43 Prague, Czech Republic Institute of Macromolecular Chemistry, Department of Supramolecular Systems and Self-Assembling Processes, Heyrovského nám. 2

• better effectiveness than other tested supramolecular hosts. Keywords: cyclodextrin; dimer; methylation; solubilization; tetracene; Introduction Cyclodextrins (CDs) are cyclic oligomers of glucose that play an important role in supramolecular chemistry [1]. The structure of any CD contains a

• hydrophobic cavity inside the molecule, while all hydrophilic hydroxy groups are arranged outside the cavity. This feature determines the main practical application of CDs as supramolecular hosts for host–guest interaction. Due to their low cost, low toxicity, and good complexation ability, they are

Supramolecular approaches to mediate chemical reactivity

• Pablo Ballester,
• Qi-Qiang Wang and
• Carmine Gaeta

Beilstein J. Org. Chem. 2022, 18, 1463–1465, doi:10.3762/bjoc.18.152

• reactions by a biomimetic approach [3][4]. Very recently, many efforts have been devoted to study supramolecular catalysis processes [5][6][7][8][9][10][11][12][13][14] in which macrocyclic hosts, self-assembled capsules and metallo-cages were employed as catalysts or nanocontainers. The primary

• characteristic of supramolecular catalysis is that the general modes of activation based on intermolecular interactions can operate on substrates in a selective way, and in confined environment, like the active site of natural enzymes [5][6][7][8][9][10][11][12][13][14]. As a result, molecular recognition of the

• substrate(s) and potentially the transition state is essential in supramolecular catalysis. Supramolecular catalysis finds inspiration in natural enzymes, which show catalytic features such as substrates and products selectivity, efficiency, geometric control, and acceleration of chemical reactivity [1]. If

1,4,6,10-Tetraazaadamantanes (TAADs) with N-amino groups: synthesis and formation of boron chelates and host–guest complexes

• Artem N. Semakin,
• Ivan S. Golovanov,
• Yulia V. Nelyubina and
• Alexey Yu. Sukhorukov

Beilstein J. Org. Chem. 2022, 18, 1424–1434, doi:10.3762/bjoc.18.148

• Tripodal molecules are widely used as chelating ligands for transition metal catalysis [1][2][3], sensors for ions and small molecules [4][5], reagents for surface grafting [6], building blocks for the construction of supramolecular structures [7], polycyclic cage molecules [8], and porous materials [9

• , 21, and 21·HCl as well as the previously described 3O-TAADs 2 do not form such host–guest complexes, although water and methanol molecules are present in their crystal lattices. Thus, the presence of amide/carbamate groups is essential for the assembly of these supramolecular structures. The

• stabilization of the complex through weak hydrophobic interactions of with tert-butyl groups of Boc. We believe that by adjustment of the substituents on the amide/carbamate groups, receptors for supramolecular sensing of alcohols [44] could be designed based on 3N-TAADs of type 4. Further research in this

Cyclodextrin-based Schiff base pro-fragrances: Synthesis and release studies

• Attila Palágyi,
• Jindřich Jindřich,
• Juraj Dian and
• Sophie Fourmentin

Beilstein J. Org. Chem. 2022, 18, 1346–1354, doi:10.3762/bjoc.18.140

• aldehyde due to the supramolecular interaction between aldehyde and β-CD cavity. It follows from Figures 5–7 that heptanal (2h) is released faster with lower pH values, whereas benzaldehyde (2d) and 5-methylfurfural (2j) show opposite trends. It can be attributed to the lower boiling point (153 °C) and

• that CD-based pro-fragrances combine a chemical barrier, as the aldehydes are linked to the CD via imine bond, and a physicochemical (supramolecular) barrier, as we established that aldehydes formed inclusion complexes in aqueous solution with β-CD. We confirmed from the NMR kinetic study of the imine

• bond decomposition that Shiff base hydrolysis is very fast in acidic conditions and slows down when going to higher pH values. Multiple headspace extraction experiments revealed the role of pH and the presence of supramolecular interaction between aldehyde and β-CD on the rate of aldehyde release from

Computational model predicts protein binding sites of a luminescent ligand equipped with guanidiniocarbonyl-pyrrole groups

• Neda Rafieiolhosseini,
• Matthias Killa,
• Thorben Neumann,
• Niklas Tötsch,
• Jean-Noël Grad,
• Alexander Höing,
• Thies Dirksmeyer,
• Jochen Niemeyer,
• Christian Ottmann,
• Shirley K. Knauer,
• Michael Giese,
• Jens Voskuhl and
• Daniel Hoffmann

Beilstein J. Org. Chem. 2022, 18, 1322–1331, doi:10.3762/bjoc.18.137

• interactions with other proteins. Here, we use a computational approach to predict the binding sites of the designed hybrid compound featuring aggregation-induced emission luminophores as a potential supramolecular ligand for 14-3-3ζ in the presence and absence of C-Raf peptides. Our results suggest that the

• prediction of two C2 related, dominating binding sites on 14-3-3ζ that may bind to two of the supramolecular ligand molecules. Keywords: AIE luminophores; fluorescence emission; guanidiniocarbonyl-pyrrole; ligand binding; 14-3-3 protein; Introduction The 14-3-3 protein family was one of the first

• option to modulate, inhibit, or stabilize protein–protein interactions (PPI) is the use of specific supramolecular ligands [7][8]. One well-known example of efficient protein binders is the so-called guanidiniocarbonyl-pyrrole (GCP) developed 20 years ago by Schmuck et al. [9]. These compounds are known

Polymer and small molecule mechanochemistry: closer than ever

• José G. Hernández

Beilstein J. Org. Chem. 2022, 18, 1225–1235, doi:10.3762/bjoc.18.128

• for polymers as force transmission media have been investigated. In 2021, Otsuka and co-workers reported supramolecular hydrogen-bonding systems as alternative mechanical force transducers [67]. Specifically, the authors synthesized tetraarylsuccinonitrile (TASN) derivatives 6 and 8. TASN is a well

• anvils, which hold promise to become standard low-molecular effective transducers of mechanical forces. This, together with the ability of ball milling to facilitate the formation of covalent and noncovalent supramolecular assemblies, could lead to the direct activation of small mechanophores via the