Multiple threading of a triple-calix[6]arene host

• Veronica Iuliano,
• Roberta Ciao,
• Emanuele Vignola,
• Carmen Talotta,
• Patrizia Iannece,
• Margherita De Rosa,
• Annunziata Soriente,
• Carmine Gaeta and
• Placido Neri

Beilstein J. Org. Chem. 2019, 15, 2092–2104, doi:10.3762/bjoc.15.207

• stereoselective formation of endo-alkyl pseudo[n]rotaxane stereoisomers. Keywords: calixarene; multiple-threading; pseudo[n]rotaxane; stereoisomers; Introduction The self-assembly [1] of smaller components to larger aggregates represents one of the most spectacular phenomena in supramolecular chemistry [2][3][4

• ]. Among the self-assembly processes, those that lead to the formation of interlocked and/or interpenetrated supramolecular structures have inspired many scientists [5][6][7][8]. The synthesis of interlocked molecules such as rotaxanes, catenanes, and high-order architectures (e.g., polyrotaxanes, suitanes

Naphthalene diimides with improved solubility for visible light photoredox catalysis

• Barbara Reiß and
• Hans-Achim Wagenknecht

Beilstein J. Org. Chem. 2019, 15, 2043–2051, doi:10.3762/bjoc.15.201

• self-assembly [43][44], as molecular sensors [45][46][47] and for organic electronics [48][49], but yet nearly completely unexplored for photoredox catalysis. Core-unsubstituted NDIs are colorless compounds with high extinction coefficients at the border between UV-A and visible light. Their

Morphology-tunable and pH-responsive supramolecular self-assemblies based on AB₂-type host–guest-conjugated amphiphilic molecules for controlled drug delivery

• Yang Bai,
• Cai-ping Liu,
• Di Chen,
• Long-hai Zhuo,
• Huai-tian Bu and
• Wei Tian

Beilstein J. Org. Chem. 2019, 15, 1925–1932, doi:10.3762/bjoc.15.188

• -responsive supramolecular self-assemblies have been constructed, the controlled drug delivery induced by morphology transitions of these supramolecular self-assemblies on the basis of host–guest-conjugated monomers (HGCMs) are few reported. In this paper, the self-assembly behaviors of AB2-type HGCMs, e.g

• stimuli-responsive supramolecular self-assemblies with regulated self-assembly morphologies due to their response to various external stimuli, such as temperature [12], light [13][14][15], redox [16][17][18], and pH [19][20]. In addition, β-cyclodextrin (β-CD), pillararene and cucurbituril have been

• -assemblies were fairly complicated, and their self-assembly behaviors could hardly effectively be regulated. Alternatively, host–guest-conjugated monomers (HGCMs) which gather host and guest units into one molecule have been studied and attracted many attentions in the field of self-assembly [35]. AB-type

Complexation of chiral amines by resorcin[4]arene sulfonic acids in polar media – circular dichroism and diffusion studies of chirality transfer and solvent dependence

• Bartosz Setner and
• Agnieszka Szumna

Beilstein J. Org. Chem. 2019, 15, 1913–1924, doi:10.3762/bjoc.15.187

• Bartosz Setner Agnieszka Szumna Institute of Organic Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, 01-224 Warsaw, Poland 10.3762/bjoc.15.187 Abstract Directional self‐assembly of conformationally well-defined complexes in polar environment is still a major challenge in supramolecular

• disintegrative for these complexes. This result is quite non-intuitive and worth attention in the context of formation of supramolecular complexes in polar environment, for which DMSO is most often a first-choice solvent. Keywords: cavitands; chirality; macrocycle; resorcin[4]arene; self-assembly

• ; supramolecular chemistry; Introduction Despite of the great progress that has been made in supramolecular chemistry in polar and aqueous media, formation of discrete ordered supramolecular associates with precise patterns of noncovalent interactions still presents a challenge [1][2]. Especially self-assembly

Norbornadiene-functionalized triazatriangulenium and trioxatriangulenium platforms

• Roland Löw,
• Talina Rusch,
• Tobias Moje,
• Fynn Röhricht,
• Olaf M. Magnussen and
• Rainer Herges

Beilstein J. Org. Chem. 2019, 15, 1815–1821, doi:10.3762/bjoc.15.175

• would have to be in the switched state 1b. The second explanation, i.e., that the mixed monolayer consists of octyl-TATA 6 and the NBD-TATA 1a, seems to be more likely, since molecule 1 decays slowly under irradiation in contact with oxygen. Previous measurements have shown that self-assembly from

• solutions containing pure and vertically functionalized TATA molecules leads to the formation of stochastically mixed monolayers with a highly ordered (√19 × √19) R23.4° superstructure [22]. This would be also expected for self-assembly from solution containing 1a and 6. The composition of the adlayer on

Complexation of 2,6-helic[6]arene and its derivatives with 1,1′-dimethyl-4,4′-bipyridinium salts and protonated 4,4'-bipyridinium salts: an acid–base controllable complexation

• Jing Li,
• Qiang Shi,
• Ying Han and
• Chuan-Feng Chen

Beilstein J. Org. Chem. 2019, 15, 1795–1804, doi:10.3762/bjoc.15.173

• methenyl groups. They have been a kind of important macrocyclic host molecules during the last decades due to their unique structures and a wide range of applications in host–guest chemistry [13][14][15][16][17][18], self-assembly [19], biomedicine [20] and materials science [21][22]. The derivatives of

Reversible end-to-end assembly of selectively functionalized gold nanorods by light-responsive arylazopyrazole–cyclodextrin interaction

• Maximilian Niehues,
• Patricia Tegeder and
• Bart Jan Ravoo

Beilstein J. Org. Chem. 2019, 15, 1407–1415, doi:10.3762/bjoc.15.140

• cycles. By the introduction of AAP, previous disassembly limitations based on the photostationary states of azobenzenes could be solved. The combination photoresponsive interaction and selectively end-functionalized nanoparticles shows significant potential in the reversible self-assembly of inorganic

• –organic hybrid nanomaterials. Keywords: cyclodextrins; gold nanorods; host–guest chemistry; light-responsive materials; molecular switches; self-assembly; Introduction Metallic nanomaterials have received intense and interdisciplinary interest due to their unique optical [1], electronic [2][3] and

• the complete surface because of its cell toxicity [17], hence strategies for replacing this coating are desirable. Host–guest chemistry is a supramolecular interaction that is tailor-made for self-assembly due to its lock–key mechanism and has been applied in our and other groups to various

Complexation of a guanidinium-modified calixarene with diverse dyes and investigation of the corresponding photophysical response

• Yu-Ying Wang,
• Yong Kong,
• Zhe Zheng,
• Wen-Chao Geng,
• Zi-Yi Zhao,
• Hongwei Sun and
• Dong-Sheng Guo

Beilstein J. Org. Chem. 2019, 15, 1394–1406, doi:10.3762/bjoc.15.139

• supramolecular cavities [25]. Calixarenes are the third generation of macrocyclic compounds composed of phenolic units bridged with methylene groups at the o-positions of phenolic hydroxy groups [9]. We have focused on molecular recognition and self-assembly of water-soluble calixarene derivatives for a long

Selective detection of DABCO using a supramolecular interconversion as fluorescence reporter

• Indrajit Paul,
• Debabrata Samanta,
• Sudhakar Gaikwad and
• Michael Schmittel

Beilstein J. Org. Chem. 2019, 15, 1371–1378, doi:10.3762/bjoc.15.137

• compounds. Keywords: copper; detection; fluorescence; interconversion; macrocycles; self-assembly; self-sorting; zinc porphyrin; Introduction Since dynamic multicomponent supramolecular structures are nowadays abundant [1][2], the weak intercomponent binding [3][4][5][6][7][8][9] is often instrumentalized

• through the expected 1H NMR pattern in particular as the signal of proton h-H in ligand 1 is shifted diagnostically from 6.28 to 6.08 ppm due to the shielding of the lutidine unit by the π-system of ligand 2 (Figure 2). Self-assembly in a similar manner using [Cu(CH3CN)4]PF6 and ligands 1, 2 and 4 (2:1:1

Self-assembly behaviors of perylene- and naphthalene-crown macrocycle conjugates in aqueous medium

• Xin Shen,
• Bo Li,
• Tiezheng Pan,
• Jianfeng Wu,
• Yangxin Wang,
• Jie Shang,
• Yan Ge,
• Lin Jin and
• Zhenhui Qi

Beilstein J. Org. Chem. 2019, 15, 1203–1209, doi:10.3762/bjoc.15.117

• absorption and fluorescence spectra of these PDI/NDI derivatives in different solvents as well as their morphologies were investigated. Keywords: aqueous medium; crown ether; macrocycle; perylene diimide derivative; self-assembly; Introduction Owing to their unique physicochemical properties, self

• -assemblies have been recognized as a type of exciting nanomaterials with tremendous potential for research and commercial applications [1][2][3][4][5][6]. Thanks to the development of supramolecular chemistry, the ordered structures could be obtained through programmed self-assembly coupled with covalent

• , little was known to the self-assembly behaviors of B21C7 crown macrocycle functionalized PDIs/NDIs in aqueous solution, even though there have been several reports about crown ether-functionalized PDIs or NDIs, which mostly focused on their interactions with metal ions [82][83][84][85]. Herein, we

Extending mechanochemical porphyrin synthesis to bulkier aromatics: tetramesitylporphyrin

• Qiwen Su and
• Tamara D. Hamilton

Beilstein J. Org. Chem. 2019, 15, 1149–1153, doi:10.3762/bjoc.15.111

• catalysis [1], photovoltaics [2], photodynamic therapy [3][4], environmental remediation [5][6], biomimetic modelling [7] and metal-organic self-assembly [8]. Porphyrins may be substituted in the meso or β-positions (Figure 1A). Tetra-meso-substituted porphyrins are usually synthesized from simple starting

Design of a double-decker coordination cage revisited to make new cages and exemplify ligand isomerism

• Sagarika Samantray,
• Sreenivasulu Bandi and
• Dillip K. Chand

Beilstein J. Org. Chem. 2019, 15, 1129–1140, doi:10.3762/bjoc.15.109

• : anion binding; double-decker cage; ligand isomerism; macrocycles; palladium; self-assembly; supramolecular; Introduction Coordination-driven self-assembly is a convenient strategy for the construction of supramolecules of desired dimensions via simple synthetic procedures. Well-defined metal–ligand

Diaminoterephthalate–α-lipoic acid conjugates with fluorinated residues

• Leon Buschbeck,
• Aleksandra Markovic,
• Gunther Wittstock and
• Jens Christoffers

Beilstein J. Org. Chem. 2019, 15, 981–991, doi:10.3762/bjoc.15.96

• solutions of compound 3 or compound 7 immediately after preparation of the gold layer. The gold substrates were left in the ethanolic solution for self-assembly over 24 h, then removed and rinsed with copious amounts of ethanol (analytical grade, Fisher Chemicals) and eventually dried in an argon stream

Halogen bonding and host–guest chemistry between N-alkylammonium resorcinarene halides, diiodoperfluorobutane and neutral guests

• Fangfang Pan,
• Mohadeseh Dashti,
• Michael R. Reynolds,
• Kari Rissanen,
• John F. Trant and
• Ngong Kodiah Beyeh

Beilstein J. Org. Chem. 2019, 15, 947–954, doi:10.3762/bjoc.15.91

• supramolecular chemistry and materials science [1][2][3]. New systems both help us to better understand the nature and impetus behind the self-assembly of these fascinating systems, while also providing new materials that can provide the basis for a wide number of applications [4][5]. Halogen bonding (XB), as a

Mechanochemistry of supramolecules

• Anima Bose and
• Prasenjit Mal

Beilstein J. Org. Chem. 2019, 15, 881–900, doi:10.3762/bjoc.15.86

• ; mechanochemistry; self-assembly; solvent-free; supramolecular; Introduction In living systems an important aspect is to create complex functional molecules from simpler units by following biomolecular mechanisms [1]. The biological assemblies for living beings are developed from processes of spontaneous self

• to form supramolecular structures through self-assembly processes by exploiting the weak or non-covalent interactions [10]. Self-assembly is a kinetically reversible process which is more efficient than traditional stepwise synthesis concerning large molecules. Some recent developments in

• supramolecular chemistry are dynamic combinatorial chemistry [11], subcomponent self-assembly approach [12][13][14], and systems chemistry [15][16][17][18], etc. There also has been growing interest towards exploration of nontraditional energy sources like visible light [19][20], microwave [21], mechanochemical

Aqueous olefin metathesis: recent developments and applications

• Valerio Sabatino and
• Thomas R. Ward

Beilstein J. Org. Chem. 2019, 15, 445–468, doi:10.3762/bjoc.15.39

• publication, catalyst 9 was used for an aqueous living ring-opening metathesis polymerization-induced self-assembly (ROMPISA). The authors demonstrated the possibility of performing living ROMP in water selecting a quaternary ammonium-based phenyl norbornene carboximide as core-forming monomer [60]. This

Application of olefin metathesis in the synthesis of functionalized polyhedral oligomeric silsesquioxanes (POSS) and POSS-containing polymeric materials

• Patrycja Żak and
• Cezary Pietraszuk

Beilstein J. Org. Chem. 2019, 15, 310–332, doi:10.3762/bjoc.15.28

• amorphous polymeric grafts in another block. Hierarchical self-assembly of rodlike copolymer was studied from the point of view of its utility in producing highly ordered 1D photonic crystals. Surface-initiated ROMP was used to grow an organic corona phase on the surface of CdSe/ZnS quantum dots [39

Olefin metathesis in multiblock copolymer synthesis

• Maria L. Gringolts,
• Yulia I. Denisova,
• Eugene Sh. Finkelshtein and
• Yaroslav V. Kudryavtsev

Beilstein J. Org. Chem. 2019, 15, 218–235, doi:10.3762/bjoc.15.21

• multiblock copolymers with respect to self-assembly. In recent years, it was demonstrated that such polymers can be prepared with many of the available techniques, including polycondensation [28], chain-shuttling polymerization [29], copper-mediated radical polymerization [30][31][32], reversible addition

Fabrication of supramolecular cyclodextrin–fullerene nonwovens by electrospinning

• Hiroaki Yoshida,
• Ken Kikuta and
• Toshiyuki Kida

Beilstein J. Org. Chem. 2019, 15, 89–95, doi:10.3762/bjoc.15.10

• its low self-assembly features in solution [15]. We recently reported that 1,1,1,3,3,3-hexafluoroisopropanol (HFIP) is a suitable solvent for CDs, and a CD/HFIP solution can be facilely electrospun into fibers at a relatively low concentration of approximately 12.5 w/v % [11], which is comparable to

Coordination-driven self-assembly of discrete Ru₆–Pt₆ prismatic cages

• Aderonke Ajibola Adeyemo and
• Partha Sarathi Mukherjee

Beilstein J. Org. Chem. 2018, 14, 2242–2249, doi:10.3762/bjoc.14.199

• Aderonke Ajibola Adeyemo Partha Sarathi Mukherjee Department of Inorganic and Physical Chemistry, Indian Institute of Science, Bangalore 560 012, India 10.3762/bjoc.14.199 Abstract The coordination-driven self-assembly of two new Ru6–Pt6 hexanuclear trigonal prismatic cages comprising arene

• spectrometry, UV–vis and infrared studies. Geometry optimization revealed the shapes and sizes of these hexanuclear prismatic cages. The combination of ruthenium and platinum metal center in a one-pot self-assembly reaction showcases the construction of aesthetically elegant heterometallic structures in

• supramolecular chemistry leading to the formation of a single major product. Keywords: arene–ruthenium(II); heterometallic cages; platinum metalloligand; self-assembly; supramolecular architectures; Introduction Coordination-driven self-assembly of discrete architectures has evolved as a unique protocol to

Tetrathiafulvalene – a redox-switchable building block to control motion in mechanically interlocked molecules

• Hendrik V. Schröder and
• Christoph A. Schalley

Beilstein J. Org. Chem. 2018, 14, 2163–2185, doi:10.3762/bjoc.14.190

Synthesis and supramolecular self-assembly of glutamic acid-based squaramides

• Juan V. Alegre-Requena,
• Marleen Häring,
• Isaac G. Sonsona,
• Alex Abramov,
• Eugenia Marqués-López,
• Raquel P. Herrera and
• David Díaz Díaz

Beilstein J. Org. Chem. 2018, 14, 2065–2073, doi:10.3762/bjoc.14.180

• derivative; organogel; self-assembly; squaramide; supramolecular gel; Introduction Since their discovery, squaramides have gained importance across different fields from chemistry to biomedicine due to their synthetic versatility and wide applicability [1]. These compounds, formed by two amine units

Coordination-driven self-assembly vs dynamic covalent chemistry: versatile methods for the synthesis of molecular metallarectangles

• Li-Li Ma,
• Jia-Qin Han,
• Wei-Guo Jia and
• Ying-Feng Han

Beilstein J. Org. Chem. 2018, 14, 2027–2034, doi:10.3762/bjoc.14.178

• desired tetranuclear metallarectangles were synthesized by using coordination-driven self-assembly of half-sandwich rhodium-based organometallic clip units and organic ligands. The reaction of such an organometallic clip with 4-formylpyridine provided a dinuclear molecular tweezer with pendant aldehyde

• self-assembly; dynamic covalent chemistry; half-sandwich rhodium complex; metallarectangles; one-pot reaction; supramolecular chemistry; Introduction Over the past two decades, supramolecular structures with organometallic half-sandwich fragments have attracted much attention, including

• coordination-driven self-assembly has been proven to be a powerful tool to construct supramolecular architectures with controlled shapes and sizes [18][19][20][21][22][23][24][25][26][27][28][29][30]. Using this strategy, a host of exciting supramolecular structures have been constructed by using two

A self-assembled photoresponsive gel consisting of chiral nanofibers

• Lei Zou,
• Dan Han,
• Zhiyi Yuan,
• Dongdong Chang and
• Xiang Ma

Beilstein J. Org. Chem. 2018, 14, 1994–2001, doi:10.3762/bjoc.14.174

• absorption spectroscopy, circular dichroism, scanning electron microscopy and rheological techniques. This work provides a new method for facile synthesis of chiro-optical gels. Keywords: chirality; nanostructure; organogel; photoresponse; self-assembly; Introduction Supramolecular gels [1][2] immobilized

• by three-dimensional networks through self-assembly have drawn significant attention in the past decades. They are normally fabricated by means of noncovalent intermolecular interactions [3], such as π–π stacking, hydrogen bonding, van der Waals forces, hydrophobic, electrostatic, host–guest and

Synthesis of new p-tert-butylcalix[4]arene-based polyammonium triazolyl amphiphiles and their binding with nucleoside phosphates

• Vladimir A. Burilov,
• Guzaliya A. Fatikhova,
• Mariya N. Dokuchaeva,
• Ramil I. Nugmanov,
• Diana A. Mironova,
• Pavel V. Dorovatovskii,
• Victor N. Khrustalev,
• Svetlana E. Solovieva and
• Igor S. Antipin

Beilstein J. Org. Chem. 2018, 14, 1980–1993, doi:10.3762/bjoc.14.173

• was elaborated for the naked-eye detection of ADP with a detection limit of 0.5 mM. Keywords: ADP; amphiphile; ATP; calix[4]arene; CuAAC; eosin Y probe; molecular recognition; polydiacetylene; self-assembly; triazole; Introduction During the last two decades many researcher groups have paid much