Radial Hetero[5]catenanes: Peripheral Isomer Sequences of the Interlocked Macrocycles

A pair of radial [5]catenanes, with either an isomeric cyclic ‐AABB‐ or ‐ABAB‐ type sequence of the interlocked β‐cyclodextrin (β‐CD) and cucurbit[6]uril (CB[6]) units, has been efficiently synthesized. Because of a marked difference in the binding strength and interlocking sequence of the peripheral macrocycles, interesting sequence‐dependent properties, characteristic of mechanically bonded macrocycles, were realized. Variable‐temperature ¹H NMR studies showed that the ‐ABAB‐ isomer has a more independent β‐CD dynamic, whereas the β‐CD motions in the ‐AABB‐ isomer are coupled. Dynamics of the pH‐insensitive β‐CD can also be further modulated upon base‐triggered mobilization of the CB[6]. These unique properties of the mechanical bond expressed in a sequence‐specific fashion and the transmission of the control on the macrocycle dynamics from one interlocked component to another, highlight the potential of similar complex hetero[n]catenanes in the design of advanced, multicomponent molecular machines.     

Co‐Conformational Distribution of Nanosized [2]Catenanes Determined by Pulse EPR Measurements

The co‐conformational ensembles of three differently sized [2]catenanes were studied by measuring pair correlation functions corresponding to the separation of nitroxide spin labels—one attached to each of the two macrocycles—with the double electron–electron resonance (DEER) experiment. A geometric model for the [2]catenanes was derived that approximates the macrocycles by circles and takes into account the topological constraint. Comparison of the experimental to the theoretically predicted pair correlation functions gives insight into the co‐conformational distribution and the size of the macrocycles. It was found that the macrocycles of the medium‐ and large‐sized catenanes in chloroform are close to fully expanded, while they are partially collapsed in glassy o‐terphenyl. For the small‐sized catenane, moderate interaction between the unsaturated sections of the macrocycles in chloroform is indicated by a slight overrepresentation of short label‐to‐label separations in the pair correlation function.     

Incorporation of a Phenanthrene Subunit into a Sapphyrin Framework: Synthesis of Expanded Aceneporphyrinoids

32‐Hetero‐5,6‐dimethoxyphenanthrisapphyrins—macrocycles that link structural features of polycylic aromatic hydrocarbons and expanded porphyrins—were obtained in a straightforward [3+1] condensation reaction of dimethoxyphenanthritripyrrane and 2,5‐bis(arylhydroxymethyl)heterocyclopentadienes. The highly folded conformation of formally 4 n π‐electron macrocycles causes them to manifest only limited macrocyclic π conjugation as explored by means of NMR spectroscopic and X‐ray structural analyses, and supported by DFT calculations. Although protonation does not change their π‐conjugation characteristics, the cleavage of ether groups at the phenanthrenylene moiety yields nonaromatic 32‐hetero‐5,6‐dioxophenanthrisapphyrins.     

π‐Conjugated [2]Catenanes Based on Oligothiophenes and Phenanthrolines: Efficient Synthesis and Electronic Properties

Novel π‐conjugated topologies based on oligothiophenes and phenanthroline have been assembled by combining their outstanding electronic and structural benefits with the specific properties of the topological structure. Macrocycles and catenanes are prepared by using an optimized protocol of transition metal‐templated macrocyclization followed by efficient Pd‐catalyzed cross‐coupling reaction steps. By using this method, [2]catenanes comprising two interlocked π‐conjugated macrocycles with different ring sizes have been synthesized. The structures of the [2]catenanes and corresponding macrocycles are confirmed by detailed ¹H NMR spectroscopy and high resolution mass spectrometry. Single crystal X‐ray structural analysis of the quaterthiophene–diyne macrocycle affords important insight into the packing features and intermolecular interaction of the new systems. The fully conjugated interlocked [2]catenanes are fully characterized by spectroscopic and electrochemical measurements.     

Dual-mode "co-conformational" switching in catenanes incorporating bipyridinium and dialkylammonium recognition sites

Three [2]catenanes and three [3]catenanes incorporating one or two pi-electron-rich macrocyclic polyethers and one pi-electron-deficient polycationic cyclophane have been synthesized in yields ranging from 4 to 38%. The pi-electron-rich macrocyclic components possess either two 1,4-dioxybenzene or two 1.5-dioxynaphthalene recognition sites. The pi-electron-deficient cyclophane components incorporate two bipyridinium and either one or two dialkylammonium recognition sites. The template-directed syntheses of these catenanes rely on i) pi...pi stacking interactions between the dioxyarene and bipyridinium recognition sites, ii) C-H...O hydrogen bonds between some of the bipyridinium hydrogen atoms and some of the polyether oxygen atoms, and iii) C-H...pi interactions between some of the dioxyarene hydrogen atoms and the aromatic spacers separating the bipyridinium units. The six catenanes were characterized by mass spectrometry and by both 1H and 13C NMR spectroscopy. The absorption spectra and the electrochemical properties of the catenanes have been investigated and compared with those exhibited by the component macrocycles and by related known catenanes. Broad and weak absorption bands in the visible region, originating from charge-transfer (CT) interactions between electron-donor and electron-acceptor units, have been observed. Such charge-transfer interactions are responsible for the quenching of the potentially fluorescent excited states of the aromatic units of the macrocyclic polyether components. The redox behavior of these novel compounds has been investigated and correlations among the observed redox potentials are illustrated and discussed. The catenanes undergo co-conformational switching upon one-electron reduction of the two bipyridinium units. One of them--in its reduced form--can be also switched by acid/base inputs and exhibits AND logic behavior. The co-conformational rearrangements induced by the redox and acid/base stimulations lend themselves to exploitation in the development of molecular-level machines and logic gates.     

Metal‐Ion‐Induced Switch of Liquid‐Crystalline Orientation of Metallomacrocycles

A new series of shape‐persistent imine‐bridged macrocycles were synthesized based on dynamic covalent chemistry. The macrocycles had an alternating sequence of dibenzothiophene and N,N′‐bis(salicylidene)‐ethylenediamine (salen) tethering branched alkyl chains. The macrocycles and tetranuclear metallomacrocycles bearing long and branched alkyl chains exhibited thermotropic columnar liquid‐crystalline phases over a wide temperature range and the metallomacrocycles greatly depended on the characteristics of the coordinated metal ions. The metal‐free macrocycle showed a liquid‐crystalline phase with a lamellar structure and poor birefringence. In sharp contrast, the macrocyclic Ni complex showed a columnar oblique liquid‐crystalline phase, whereas the Pd and Cu complexes showed columnar liquid‐crystalline phases with a lamellar structure. The macroscopic organization and thermal properties of the corresponding liquid‐crystalline metallomacrocycles were significantly dependent on the subtle structural differences among the planar macrocycles, which were revealed by single‐crystal X‐ray crystallographic analysis of the macrocycles with shorter alkyl chains.     

Metallomacrocycles with a Difference: Macrocyclic Complexes with Exocyclic Ruthenium(II)‐Containing Domains

The templated synthesis of organic macrocycles containing rings of up to 96 atoms and three 2,2′‐bipyridine (bpy) units is described. Starting with the bpy‐centred ligands 5,5′‐bis[3‐(1,4‐dioxahept‐6‐enylphenyl)]‐2,2′‐bipyridine and 5,5′‐bis[3‐(1,4,7‐trioxadec‐9‐enylphenyl)]‐2,2′‐bipyridine, we have applied Grubbs’ methodology to couple the terminal alkene units of the coordinated ligands in [FeL₃]²⁺ complexes. Hydrogenation and demetallation of the iron(II)‐containing macrocyclic complexes results in the isolation of large organic macrocycles. The latter bind {Ru(bpy)₂} units to give macrocyclic complexes with exocyclic ruthenium(II)‐containing domains. The complex [Ru(bpy)₂(L)]²⁺ (isolated as the hexafluorophosphate salt), in which L=5,5′‐bis[3‐(1,4,7,10‐tetraoxatridec‐12‐enylphenyl)]‐2,2′‐bipyridine, undergoes intramolecular ring‐closing metathesis to yield a macrocycle which retains the exocyclic {Ru(bpy)₂} unit. The poly(ethyleneoxy) domains in the latter macrocycle readily scavenge sodium ions, as proven by single‐crystal X‐ray diffraction and atomic absorption spectroscopy data for the bulk sample. In addition to the new compounds, a series of model complexes have been fully characterized, and representative single‐crystal X‐ray structural data are presented for iron(II) and ruthenium(II) acyclic and macrocyclic species.     

Macrocycles IV. Macrocyclic polylactones as bifunctional monomers for polycondensations

Tin containing macrocyclic polylactones were prepared by di-n-butyl-2-stanna-1,3-dioxepane-initiated polymerizations of ε-caprolactone in bulk. The average ring size was varied from 10 to 100 monomer units via the monomer/initiator (M/I) ratio. Addition of terephthaloyl or sebacoyl chloride to the in situ prepared macrocycles yielded polycondensates under elimination of di-n-butyl tin dichloride. The molecular weights increased with the reaction temperature (e.g., 80–140°C) and with the size of the macrocycles. Number-average molecular weights (M_ns) up to 90,000 and polydispersities between 1.65 and 2.0 were obtained. Further polycondensations were conducted with isophthaloyl chloride, 4,4′-biphenyldicarbonylchloride and 4,4′-phenylenebisacryloylchloride. Several polycondensations were performed with macrocyclic poly (δ-valerolactone) and poly (β-D ,L -butyrolactone). In those cases the increase of the molecular weight was lower. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1373–1378, 1998     

Prismarene: An Emerging Naphthol‐Based Macrocyclic Arene

Phenol‐based macrocyclic arenes have been widely used in supramolecular chemistry, significantly enriching the toolbox of the field. In contrast, naphthol‐based macrocyclic arenes are rather underdeveloped. Very recently, Gaeta and co‐workers successfully synthesized such macrocycles (referred to as prism[n]arenes) with good guest‐binding ability by reacting 2,6‐dimethoxynaphthalene with paraformaldehyde under optimized conditions. In view of the simple synthesis and good host–guest chemistry, we anticipate that this macrocycle will find similar success and wide applications as the phenol‐based macrocyclic arenes.     

Effects of Axle‐Core,Macrocycle, and Side‐Station Structures on the Threading and Hydrolysis Processes of Imine‐Bridged Rotaxanes

Imine‐bridged rotaxanes are a new type of rotaxane in which the axle and macrocyclic ring are connected by imine bonds. We have previously reported that in imine‐bridged rotaxane 5 , the shuttling motion of the macrocycle could be controlled by changing the temperature. In this study, we investigated how the axle and macrocycle structures affect the construction of the imine‐bridged rotaxane as well as the dynamic equilibrium between imine‐bridged rotaxane 5 and [2]rotaxane 7 by using various combinations of axles ( 1 A , B ), macrocycles ( 2 a – e ), and side‐stations (XYL and TEG). In the threading process, the flexibility of the macrocycle and the substituent groups at the para position of the aniline moieties affect the preparation of the threaded imines. The size of the imine‐bridging station and the macrocyclic tether affects the hydrolysis of the imine bonds under acidic conditions.     

Spectroscopic and Electrochemical Properties of Catenanes Containing the 2,7-Diazapyrenium Unit

Abstract

The spectroscopic and electrochemical properties of two cyclophanes containing one and, respectively, two 2,7-diazapyrenium electron-acceptor units, and of their [2]catenanes with macrocycles containing two dioxybenzene or dioxynaphthalene electrondonor units have been investigated. The absorption spectra of the catenanes show weak and broad bands in the visible region, assigned to charge-transfer (CT) interactions. The very strong and structured fluorescence (298 K) and the structured fluorescence and phosphorescence (77 K) of the diazapyrenium unit are maintained in the two cyclophanes, but they are no longer present in the [2]catenanes, presumably because of a quenching process caused by the lower energy CT excited states. Each diazapyrenium unit undergoes two distinct reduction processes - only the first one of which is fully reversible - that are hardly affected at all when the diazapyrenium units are incorporated in a cyclophane. In the [2]catenanes, the CT interaction displaces the reduction processes of the diazapyrenium units toward more negative potentials. The results obtained for the diazapyrenium and previously investigated 4,4′-bipyridinium salts, selected cyclophane derivatives, and some [2]catenanes obtained by interlocking the cyclophanes with macrocycles containing two dioxyaromatic electron-donor units are compared and discussed.     

Trinuclear Cage‐Like ZnII Macrocyclic Complexes: Enantiomeric Recognition and Gas Adsorption Properties

Three zinc(II) ions in combination with two units of enantiopure [3+3] triphenolic Schiff‐base macrocycles 1 , 2 , 3 , or 4 form cage‐like chiral complexes. The formation of these complexes is accompanied by the enantioselective self‐recognition of chiral macrocyclic units. The X‐ray crystal structures of these trinuclear complexes show hollow metal–organic molecules. In some crystal forms, these barrel‐shaped complexes are arranged in a window‐to‐window fashion, which results in the formation of 1D channels and a combination of both intrinsic and extrinsic porosity. The microporous nature of the [Zn₃ 1 ₂] complex is reflected in its N₂, Ar, H₂, and CO₂ adsorption properties. The N₂ and Ar adsorption isotherms show pressure‐gating behavior, which is without precedent for any noncovalent porous material. A comparison of the structures of the [Zn₃ 1 ₂] and [Zn₃ 3 ₂] complexes with that of the free macrocycle H₃ 1 reveals a striking structural similarity. In H₃ 1 , two macrocyclic units are stitched together by hydrogen bonds to form a cage very similar to that formed by two macrocyclic units stitched together by Zn^II ions. This structural similarity is manifested also by the gas adsorption properties of the free H₃ 1 macrocycle. Recrystallization of [Zn₃ 1 ₂] in the presence of racemic 2‐butanol resulted in the enantioselective binding of (S)‐2‐butanol inside the cage through the coordination to one of the Zn^II ions.     

Intense Molar Circular Dichroism in Fully Conjugated All-Carbon Macrocyclic 1,3-Butadiyne Linked pseudo-meta [2.2]Paracyclophanes**

The synthetic access to macrocyclic molecular topologies with interesting photophysical properties has greatly improved thanks to the successful implementation of organic and inorganic corner units. Based on recent reports, we realized that pseudo-meta [2.2]paracyclophanes (PCPs) might serve as optimal corner units for constructing 3D functional materials, owing to their efficient electronic communication, angled substituents and planar chirality. Herein, we report the synthesis, characterization and optical properties of four novel all-carbon enantiopure macrocycles bearing three to six pseudo-meta PCPs linked by 1,3-butadiyne units. The macrocycles were obtained by a single step from enantiopure, literature-known dialkyne pseudo-meta PCP and were unambiguously identified and characterized by state of the art spectroscopic methods and in part even by x-ray crystallography. By comparing the optical properties to relevant reference compounds, it is shown that the pseudo-meta PCP subunit effectively elongates the conjugated system throughout the macrocyclic backbone, such that already the smallest macrocycle consisting of only three subunits reaches a polymer-like conjugation length. Additionally, it is shown that the chiral pseudo-meta PCPs induce a remarkable chiroptical response in the respective macrocycles, reaching unprecedented high molar circular dichroism values for all-carbon macrocycles of up to 1307 L mol⁻¹ cm⁻¹.     

Polylactones, 46. Telechelic polylactones having amino acid,dipeptide or penicilline endgroups via macrocyclic polymerization

Using 2‐stanna‐1,3‐dioxepane (DSDOP) as cyclic initiator either neat ε‐caprolactone (ε‐CL) or mixtures of ε‐CL and L ‐lactide were polymerized in bulk. The resulting tin‐containing macrocyclic polylactones were reacted with an excess of N‐protected amino acid or dipeptide 4‐chlorothiophenyl esters. It was shown that the coupling of amino acid thioaryl esters and tin‐containing macrocycles does not involve any racemization. The cleavage of Boc groups with trifluoroacetic acid proved to be feasible but not the hydrogenolytic cleavage of the Z‐group.     

Effect of metallosupramolecular polymer concentration on the synthesis of poly[n]catenanes

Poly[n]catenanes are a class of polymers that are composed entirely of interlocked rings. One synthetic route to these polymers involves the formation of a metallosupramolecular polymer (MSP) that consists of alternating units of macrocyclic and linear thread components. Ring closure of the thread components has been shown to yield a mixture of cyclic, linear, and branched poly[n]catenanes. Reported herein are investigations into this synthetic methodology, with a focus on a more detailed understanding of the crude product distribution and how the concentration of the MSP during the ring closing reaction impacts the resulting poly[n]catenanes. In addition to a better understanding of the molecular products obtained in these reactions, the results show that the concentration of the reaction can be used to tune the size and type of poly[n]catenanes accessed. At low concentrations the interlocked product distribution is limited to primarily oligomeric and small cyclic catenanes . However, the same reaction at increased concentration can yield branched poly[n]catenanes with an ca. 21 kg mol⁻¹, with evidence of structures containing as many as 640 interlocked rings (1000 kg mol⁻¹).

Concentration of the metallosupramolecular polymer precursors have a significant effect on the architecture and size of the resulting poly[n]catenanes formed via a ring closing metathesis step.     

When Self‐Assembly Fails: Stepwise Metal‐Directed Synthesis of [2]Catenanes

On the attempted synthesis of a series of homo‐ and heterotrimetallic [2]catenanes by the self‐assembly of a 2‐(pyridin‐4‐ylmethyl)‐2,7‐diazapyrenium ligand, (ethylenediamine)palladium(II) or platinum(II) nitrate, and a dioxoaryl bis(N‐monoalkyl‐4,4′‐bipyridinium) salt as building blocks, both the one‐pot direct self‐assembly of the components and the so called “magic ring” approach fail to produce the expected trinuclear [2]catenanes under thermodynamically driven conditions. However, one of the target supramolecules is obtained by following a stepwise protocol, consisting of the threading of a dinuclear Pt^II metallacycle and the dioxoaryl bis(N‐monoalkyl‐4,4′‐bipyridinium) axle, followed by kinetically controlled Pt^II‐directed cyclization of the corresponding pseudorotaxane.     

Synthesis of Giant π-Extended Molecular Macrocyclic Rings as Finite Models of Carbon Nanotubes Displaying Enriched Size-Dependent Physical Properties

Bottom-up synthesis of π-extended macrocyclic carbon rings is promising for constructing length- and diameter-specific carbon nanotubes (CNTs). However, it is still a great challenge to realize size-controllable giant carbon macrocycles. Herein, a tunable synthesis of curved nanographene-based giant π-extended macrocyclic rings (CHBC[n]s; n=8, 6, 4), as finite models of armchair CNTs, is reported. Among them, CHBC[8] contains 336 all-carbon atoms and is the largest cyclic conjugated molecular CNT segment ever reported. CHBC[n]s were systematically characterized by various spectroscopic methods and applied in photoelectrochemical cells for the first time. This revealed that the proton chemical shifts, fluorescence, and electronic and photoelectrical properties of CHBC[n]s are highly dependent on the macrocycle diameter. The tunable bottom-up synthesis of giant macrocyclic rings could pave the way towards large π-extended diameter- and chirality-specific CNT segments.     

Cooperative Self‐Assembly of Pyridine‐2,6‐Diimine‐Linked Macrocycles into Mechanically Robust Nanotubes

Nanotubes assembled from macrocyclic precursors offer a unique combination of low dimensionality, structural rigidity, and distinct interior and exterior microenvironments. Usually the weak stacking energies of macrocycles limit the length and mechanical strength of the resultant nanotubes. Imine‐linked macrocycles were recently found to assemble into high‐aspect ratio (>10³), lyotropic nanotubes in the presence of excess acid. Yet these harsh conditions are incompatible with many functional groups and processing methods, and lower acid loadings instead catalyze macrocycle degradation. Here we report pyridine‐2,6‐diimine‐linked macrocycles that assemble into high‐aspect ratio nanotubes in the presence of less than 1 equiv of CF₃CO₂H per macrocycle. Analysis by gel permeation chromatography and fluorescence spectroscopy revealed a cooperative self‐assembly mechanism. The low acid concentrations needed to induce assembly enabled nanofibers to be obtained by touch‐spinning, which exhibit higher Young's moduli (1.33 GPa) than many synthetic polymers and biological filaments. These findings represent a breakthrough in the design of inverse chromonic liquid crystals, as assembly under such mild conditions will enable the design of structurally diverse and mechanically robust nanotubes from synthetically accessible macrocycles.     

A Macrocyclic Peptide Library with a Structurally Constrained Cyclopropane‐containing Building Block Leads to Thiol‐independent Inhibitors of Phosphoglycerate Mutase

Here we report the construction of an mRNA‐encoded library of thioether‐closed macrocyclic peptides by using an N‐chloroacetyl‐cyclopropane‐containing exotic initiator whose structure is more constrained than the ordinary N‐chloroacetyl‐α‐amino acid initiators. The use of such an initiator has led to a macrocycle library with significantly suppressed population of lariat‐shaped species compared with the conventional libraries. We previously used a conventional library and identified a small lariat thioether‐macrocycle with a tail peptide with a C‐terminal free Cys whose sidechain plays an essential role in potent inhibitory activity against a parasitic model enzyme, phosphoglycerate mutase. On the other hand, the cyclopropane‐containing macrocycle library has yielded a larger thioether‐macrocycle lacking a free Cys residue, which exhibits potent inhibitory activity to the same enzyme with a different mode of action. This result indicates that such a cyclopropane‐containing macrocycle library would allow us to access mechanistically distinct macrocycles.     

Building [2]Catenanes around a Tris(diimine)ruthenium(2+) ([Ru(diimine)3]2+) Complex Core Used as Template

In the course of the last two decades, the use of transition metals as templates for constructing catenanes has almost exclusively been restricted to tetrahedral copper(I). The present work is dealing with an octahedral metal, ruthenium(II), coordinated to three bidentate chelates. Incorporation of two chelates (1,10‐phenanthroline) in a ring allows to prepare a C₂‐symmetric ruthenium complex, the two chelates being disposed cis to one another (see 14 ²⁺ and 16 ²⁺ in Scheme 5 and 6, resp.). The ring is large enough to accomodate a third chelate, thus allowing the metal‐directed threading of a long fragment containing the third chelate (2,2′‐bipyridine derivative; see 23 ²⁺ and 24 ²⁺ in Scheme 8). The last step consists of a ring‐closing metathesis reaction with two terminal olefins. The two ruthenium(II)‐complexed catenanes 25 ²⁺ and 26 ²⁺ were prepared by using this strategy, each containing a 42‐membered ring interlocked to a larger macrocycle (50‐ or 63‐membered ring) incorporating the two 1,10‐phenanthroline chelates. It is expected that these catenanes can be set in motion under light‐irradiation, thus behaving as photochemically driven molecular machines.