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

• covalently linked polymers. So far, the design of such monomers has relied heavily on three-dimensional macrocycles, and the use of two-dimensional shape-persistent macrocycles for this purpose remains rather rare. Here, we demonstrate a dimerization motif based on a hydrogen-bonded macrocycle that can be

• polymerization concentration of 17 μM. These polymers were highly concentration-dependent. Establishing this new dimerization motif with shape-persistent H-bonded macrocycles widens the scope of noncovalent building blocks for supramolecular polymers and augurs well for the future development of functional

• materials. Keywords: hydrogen-bonded macrocycle; orthogonal self-assembly; shape-persistent; supramolecular polymer; Introduction Host–guest interactions, particularly those involving macrocycles as hosts [1], have found a myriad of applications in supramolecular chemistry [2][3][4] owing to their ability

Nanopatterns of arylene–alkynylene squares on graphite: self-sorting and intercalation

• Tristan J. Keller,
• Joshua Bahr,
• Kristin Gratzfeld,
• Nina Schönfelder,
• Marcin A. Majewski,
• Marcin Stępień,
• Sigurd Höger and
• Stefan-S. Jester

Beilstein J. Org. Chem. 2019, 15, 1848–1855, doi:10.3762/bjoc.15.180

• , guest molecules can act as alien species that affect the morphologies of intermolecular nanopores [12]. Another approach for the formation of nanopores relies on the physisorption of shape-persistent macrocycles [13][14]. While there are examples for the deposition of organic molecules into rigid

• the solubility limit can be overcome by appropriate substitution. We recently investigated self-assembled nanoporous networks of shape-persistent macrocycles in which dithiophene-based corner building blocks connect linear oligo(phenylene–ethynylene–butadiynylene)s (OPEBs) to form molecular polygons

• other words, either alkyl/alkoxy chains of the same or different length(s) will interdigitate, which corresponds to narcisstic self-sorting or social self-sorting, respectively [26]. Results and Discussion Here, we report on the synthesis and supramolecular nanopatterns of shape-persistent arylene

Interactions between shape-persistent macromolecules as probed by AFM

• Johanna Blass,
• Jessica Brunke,
• Franziska Emmerich,
• Cédric Przybylski,
• Vasil M. Garamus,
• Artem Feoktystov,
• Roland Bennewitz,
• Gerhard Wenz and
• Marcel Albrecht

Beilstein J. Org. Chem. 2017, 13, 938–951, doi:10.3762/bjoc.13.95

• -Str. 1, 21502 Geesthacht, Germany Jülich Centre for Neutron Science (JCNS) at Heinz Maier-Leibnitz Zentrum (MLZ), Forschungszentrum Jülich GmbH, Lichtenbergstr. 1, 85748 Garching, Germany 10.3762/bjoc.13.95 Abstract Water-soluble shape-persistent cyclodextrin (CD) polymers with amino-functionalized

• ; shape persistent polymers; Introduction Shape-persistence is an important key feature in self-organisation strategies of supramolecular building blocks resulting in high structural perfection of the obtained molecular assemblies [1], such as shape persistent macrocycles, cage compounds or rotaxanes [2

• ][3][4]. Especially shape-persistent polymers are of significant scientific interest as their defined structural characteristics offer various applications as sensor materials, biomimetic filaments or organic electronics [5][6][7]. Furthermore, compared to polymers with flexible chains, shape

Creating molecular macrocycles for anion recognition

• Amar H. Flood

Beilstein J. Org. Chem. 2016, 12, 611–627, doi:10.3762/bjoc.12.60

• Amar H. Flood Department of Chemistry, Indiana University, Bloomington, IN 47405, USA 10.3762/bjoc.12.60 Abstract The creation and functionality of new classes of macrocycles that are shape persistent and can bind anions is described. The genesis of triazolophane macrocycles emerges out of

• binding, which also provides a basis for computer-aided receptor design. The fact that triazolophanes are shape-persistent helps immensely for finding agreement between experiment and theory. Working in collaboration with Krishnan Raghavachari, we investigated some of the early ideas about how the

Assembly of synthetic Aβ miniamyloids on polyol templates

• Sebastian Nils Fischer and
• Armin Geyer

Beilstein J. Org. Chem. 2015, 11, 2646–2653, doi:10.3762/bjoc.11.284

• peptides, which are linked to the template as boronic esters. A shape-persistent template is necessary which offers the correct spacing between Aβ strands to allow for their preferred cross-β-sheet contacts. The modular assembly of peptides on a template is expected to access synthetic Aβ miniamyloids with

Articulated rods – a novel class of molecular rods based on oligospiroketals (OSK)

• Pablo Wessig,
• Roswitha Merkel and
• Peter Müller

Beilstein J. Org. Chem. 2015, 11, 74–84, doi:10.3762/bjoc.11.11

• functionalizations in terminal positions. First applications were presented with pyrene, cinnamoyl and anthracenyl labelled ARs. Keywords: articulated rods; click chemistry; molecular rods; oligospiroketals; pyrene excimer; Introduction One of the basic principles in living nature is based on shape-persistent and

Mono- and multilayers of molecular spoked carbazole wheels on graphite

• Stefan-S. Jester,
• A. Vikas Aggarwal,
• Daniel Kalle and
• Sigurd Höger

Beilstein J. Org. Chem. 2014, 10, 2783–2788, doi:10.3762/bjoc.10.295

• ]. They can be viewed as shape-persistent arylene–alkynylene macrocycles in which the intraannular spoke system increases the stiffness (persistence length) of the ring. They are non-collapsible monodisperse cyclooligomers with a fixed and predictable conformation, and their side-chain substitution

• guarantees their solubility in organic media. Our previous works on freely rotating chains of rigid rod segments and on shape-persistent macrocycles [6][7] have recently led us to a set of molecular polygons (macrocycles) of discrete sizes and symmetries, e.g., triangles, squares, pentagons, and hexagons [8

• Stefan-S. Jester A. Vikas Aggarwal Daniel Kalle Sigurd Hoger Kekulé-Institut für Organische Chemie und Biochemie, Rheinische Friedrich-Wilhelms-Universität Bonn, Gerhard-Domagk-Str. 1, 53121 Bonn, Germany 10.3762/bjoc.10.295 Abstract Self-assembled monolayers of a molecular spoked wheel (a shape

Self-assembled monolayers of shape-persistent macrocycles on graphite: interior design and conformational polymorphism

• Joscha Vollmeyer,
• Friederike Eberhagen,
• Sigurd Höger and
• Stefan-S. Jester

Beilstein J. Org. Chem. 2014, 10, 2774–2782, doi:10.3762/bjoc.10.294

• Joscha Vollmeyer Friederike Eberhagen Sigurd Hoger Stefan-S. Jester Kekulé-Institut für Organische Chemie und Biochemie, Rheinische Friedrich-Wilhelms-Universität Bonn, Gerhard-Domagk-Str. 1, 53121 Bonn, Germany 10.3762/bjoc.10.294 Abstract Three shape-persistent naphthylene–phenylene–acetylene

• macrocycle distances are mainly determined by their size and symmetry. This is an excellent example that the graphite acts as a template for the macrocycle organization independent from their specific interior. Keywords: conformational polymorphism; self-assembled monolayers; shape-persistent macrocycles

• implemented into the adlayer building blocks. An efficient functionality of such architectures will essentially rely on a precise control of the orientation and distribution of the molecules on the surface that is summarized in the field of 2D supramolecular engineering [1][2]. Shape-persistent arylene

Homochiral BINOL-based macrocycles with π-electron-rich, electron-withdrawing or extended spacing units as receptors for C₆₀

• Marco Caricato,
• Silvia Díez González,
• Idoia Arandia Ariño and
• Dario Pasini

Beilstein J. Org. Chem. 2014, 10, 1308–1316, doi:10.3762/bjoc.10.132

• ; supramolecular chemistry; Introduction Shape persistent macrocycles are carbon-based nanomaterials and are more and more in demand. They enrich the molecular toolkit available to a variety of disciplines, e.g., supramolecular chemistry and materials science [1][2][3][4]. Shape persistency properties are

The influence of intraannular templates on the liquid crystallinity of shape-persistent macrocycles

• Joscha Vollmeyer,
• Ute Baumeister and
• Sigurd Höger

Beilstein J. Org. Chem. 2014, 10, 910–920, doi:10.3762/bjoc.10.89

• 4, 06120 Halle (Saale), Germany 10.3762/bjoc.10.89 Abstract A series of shape-persistent phenylene–ethynylene–naphthylene–butadiynylene macrocycles with different extraannular alkyl groups and intraannular bridges is synthesized by oxidative Glaser-coupling of the appropriate precursors. The

• planar. Keywords: discotic liquid crystals; shape-persistent macrocycles; templates; X-ray scattering; Introduction The supramolecular chemistry of shape-persistent macrocycles has enormously expanded during the past several years [1][2][3][4][5][6]. It covers the non-covalent interaction between the

• compound molecules and also the interaction between the macrocycles and appropriate partners. For example, the 2D organization of shape-persistent macrocycles at suitable surfaces leads to long-range ordered patterns with nanoscale lattice parameters and, moreover, even to the epitaxial absorption of

Synthesis, photophysical and electrochemical characterization of terpyridine-functionalized dendritic oligothiophenes and their Ru(II) complexes

• Amaresh Mishra,
• Elena Mena-Osteritz and
• Peter Bäuerle

Beilstein J. Org. Chem. 2013, 9, 866–876, doi:10.3762/bjoc.9.100

• -transfer processes. A series of shape-persistent all-thiophene dendrons and dendrimers were recently introduced by Advincula et al. [39][40] and us [41][42]. These dendritic oligothiophenes are excellent model compounds for the study of fundamental photophysical and electronic properties. Furthermore, core

• complexes. This trend was further reflected by the decrease in the band gap with increasing generation. Conclusion The synthesis and characterization of shape-persistent oligothienylene-ethynylene dendrons of the first and second generation, which were core-functionalized with terpyridine (tpy) chelating

The chemistry of bisallenes

• Henning Hopf and
• Georgios Markopoulos

Beilstein J. Org. Chem. 2012, 8, 1936–1998, doi:10.3762/bjoc.8.225

Synthesis and anion recognition properties of shape-persistent binaphthyl-containing chiral macrocyclic amides

• Marco Caricato,
• Nerea Jordana Leza,
• Claudia Gargiulli,
• Giuseppe Gattuso,
• Daniele Dondi and
• Dario Pasini

Beilstein J. Org. Chem. 2012, 8, 967–976, doi:10.3762/bjoc.8.109

• , Italy INSTM Research Unit, Department of Chemistry, University of Pavia, 27100 Pavia, Italy 10.3762/bjoc.8.109 Abstract We report on the synthesis and characterization of novel shape-persistent, optically active arylamide macrocycles, which can be obtained using a one-pot methodology. Resolved, axially

Molecular switches and cages

• Dirk Trauner

Beilstein J. Org. Chem. 2012, 8, 870–871, doi:10.3762/bjoc.8.97

• (Rück-Braun, Hoppmann). Two reviews discuss cis-azobenzenes with rapid thermal isomerization kinetics (Velasco), and highlight the azobenzene moiety as one of the smallest light-driven molecular motors conceivable (Merino). Issues of bistability are also addressed in an account on shape-persistent

Self-assembly of Ru₄ and Ru₈ assemblies by coordination using organometallic Ru(II)₂ precursors: Synthesis, characterization and properties

• Sankarasekaran Shanmugaraju,
• Dipak Samanta and
• Partha Sarathi Mukherjee

Beilstein J. Org. Chem. 2012, 8, 313–322, doi:10.3762/bjoc.8.34

• , we and others have recently reported several shape-persistent discrete macrocycles/cages using half-sandwich octanuclear Ru(II) piano-stool complexes in combination with polypyridyl or polycarboxylate donors [6][7][8][9][10]. Ligands with an imidazole functionality are of considerable interest due to

The interplay of configuration and conformation in helical perylenequinones: Insights from chirality induction in liquid crystals and calculations

• Elisa Frezza,
• Silvia Pieraccini,
• Stefania Mazzini,
• Alberta Ferrarini and
• Gian Piero Spada

Beilstein J. Org. Chem. 2012, 8, 155–163, doi:10.3762/bjoc.8.16

• material science [3][4]. In this context, one of the major research lines focuses on the investigation of the chirality transfer between “shape persistent” dopants and nematic solvents [2][5][6][7][8][9][10][11]. Thus, the chirality amplification from the molecular to mesophase level can be exploited for

Low temperature enantiotropic nematic phases from V-shaped, shape-persistent molecules

• Matthias Lehmann and
• Jens Seltmann

Beilstein J. Org. Chem. 2009, 5, No. 73, doi:10.3762/bjoc.5.73

• Matthias Lehmann Jens Seltmann Institute of Chemistry, Chemnitz University of Technology, Straße der Nationen 62, 09111 Chemnitz, Germany 10.3762/bjoc.5.73 Abstract A series of V-shaped, shape-persistent thiadiazole nematogens, based on an oligo(phenylene ethynylene) scaffold with ester groups

• design a shape-persistent molecular scaffold of type I (Figure 2) based on oligo(phenylene ethynylene) building blocks. These molecules show liquid crystal behaviour only with a flat bending unit possessing a dipole along the apex of the mesogen, sufficiently long aliphatic chains R and at least one

• of a series of thiadiazoles of general structure II is presented and the successful approach to low temperature, enantiotropic nematic liquid crystals in the family of bent-shaped oligo(phenylene ethynylenes) will be discussed. Results and Discussion Synthesis The shape-persistent arms of the new

Shape- persistent macrocycle with intraannular alkyl groups: some structural limits of discotic liquid crystals with an inverted structure

• Sigurd Höger,
• Jill Weber,
• Andreas Leppert and
• Volker Enkelmann

Beilstein J. Org. Chem. 2008, 4, No. 1, doi:10.1186/1860-5397-4-1

• -Planck-Institut für Polymerforschung, Ackermannweg 10, 55128 Mainz, Germany 10.1186/1860-5397-4-1 Abstract The synthesis and thermal properties of new shape-persistent macrocycles of different sizes decorated with intraannular alkyl chains are described. The alkyl chain length is in all cases sufficient

• than spheres. For the larger macrocycles it is shown that longer adaptable substituents decrease the phase transition temperatures compared to previously described structures. Background During the past several years, the interest in the design and study of shape-persistent macrocycles with an

• , the supramolecular chemistry of rigid rings is currently investigated with considerable effort. For example, shape-persistent macrocycles can act as host structures for appropriate guest molecules; they can form 1D aggregates (in solution or gas phase) or regular 2D lattices after deposition at