Helical Bilayer Nonbenzenoid Nanographene Bearing a [10]Helicene with Two Embedded Heptagons

The precision synthesis of helical bilayer nanographenes (NGs) with new topology is of substantial interest because of their exotic physicochemical properties. However, helical bilayer NGs bearing non-hexagonal rings remain synthetically challenging. Here we present the efficient synthesis of the first helical bilayer nonbenzenoid nanographene ( HBNG1 ) from a tailor-made azulene-embedded precursor, which contains a novel [10]helicene backbone with two embedded heptagons. Single-crystal X-ray analysis reveals its highly twisted bilayer geometry with a record small interlayer distance of 3.2 Å among the reported helical bilayer NGs. Notably, the close interlayer distance between the two layers offers intramolecular through-space conjugation as revealed by in situ spectroelectrochemistry studies together with DFT simulations. Furthermore, the chiroptical properties of the P/M enantiomers of HBNG1 are also evaluated by circular dichroism and circularly polarized luminescence.     

A Fourfold Gold(I)−Aryl Macrocycle with Hyperbolic Geometry and its Reductive Elimination to a Carbon Nanoring Host

An ethylene glycol-decorated [6]cyclo-meta-phenylene (CMP) macrocycle was synthesized and utilized as a subunit to construct a fourfold Au^I₂−aryl metallacycle with an overall square arrangement. The corners consist of rigid dinuclear gold(I) complexes previously known to form only triangular metallacycles. The interplay between the conformational flexibility of the [6]CMP macrocycle and the rigid dinuclear gold(I) moieties enable the square geometry, as revealed by single-crystal X-ray diffraction. The formation of the gold complex shows size-selectivity compared to an alternative route using platinum(II) corner motifs. Upon reductive elimination, an all-organic ether-decorated carbon nanoring was obtained. Investigation as a host for the complexation of large guest molecules with a suitable convex π-surfaces was accomplished using isothermal NMR binding titrations. Association constants for [6]cycloparaphenylene ([6]CPP), [7]CPP, C₆₀, and C₇₀ were determined.     

Macrocycle-Based Crystalline Supramolecular Assemblies Built with Intermolecular Charge-Transfer Interactions

Synthetic macrocycles have served as principal tools for supramolecular chemistry, have greatly extended the scope of organic charge transfer (CT) complexes, and have proved to be of great practical value in the solid state during the past few years. In this Minireview, we summarize the research progress on the macrocycle-based crystalline supramolecular assemblies primarily driven by intermolecular CT interactions (a.k.a. macrocycle-based crystalline CT assemblies, MCCAs for short), which are classified by their donor–acceptor (D-A) constituent elements, including simplex macrocyclic hosts, heterogeneous macrocyclic hosts, and host–guest D-A pairs. Particular attention will be focused on their diverse functions and applications, as well as the underlying CT mechanisms from the perspective of crystal engineering. Finally, the remaining challenges and prospects are outlined.     

Bicyclo[1.1.1]pentane Embedded in Porphyrinoids**

We report a two-step approach to obtain synthetically versatile bicyclo[1.1.1]pentane (BCP) derivatives using Grignard reagents. This method allows the incorporation of BCP units in tetrapyrrolic macrocycles and the synthesis of a new class of calix[4]pyrrole analogues by replacing two bridging methylene groups with two BCP units. In addition, a doubly N-confused system was also formed in the presence of electron-withdrawing substituents at the BCP bridgeheads. The pyrrole rings in BCP containing macrocycles exist in 1,3-alternate or αβαβ conformations, as observed from single-crystal X-ray diffraction analyses and 2D NMR spectroscopy.     

Akaike's Information Criterion for Stoichiometry Inference of Supramolecular Complexes

“How do we decide the stoichiometry of host–guest complexes?” This question has long been answered by the Job plot since its first report in 1928. However, as the Job plot was claimed to be misleading in 2016, the question became an open question again and called for renewed investigations. An information-theoretic approach, called Akaike's information criterion, is introduced in this study to select the best model of host–guest complexes, which can rank the models with weight of evidence. A few test cases with unique cylindrical hosts were examined to demonstrate the applicability of the information-theoretic method. Consequently, reasonable views over the thermodynamic behaviors of dumbbell-and-cylinder complexes were obtained. Akaike's information criterion can be a useful and superior alternative to statistical null hypothesis testing, which was proposed as a remedy in place of the Job plot.     

Cycling a Tether into Multiple Rings: Pt-Bridged Macrocycles for Differentiated Guest Recognition,Pseudorotaxane Transformations,and Guest Capture and Release

Macrocycle engineering is a key topic in supramolecular chemistry. When synthesizing a ring, one can obtain either complex mixtures of macrocycles of different sizes or a single ring if a template is utilized. Here, we unite these approaches along with post-synthetic modifications to transform a single tether into multiple rings—up to five per tether. The macrocycles contain two bridged phenylpyridine ligands that are connected through a Pt atom, which defines the rings’ shape, size, and host activity. All rings undergo redox reactions (between Pt^II and Pt^IV) that allow for large conformational changes. Their reactivity, together with their host performance, is a convenient way to control the capture and release of guests, to mediate ring transformations, and to control pseudorotaxane-to-pseudorotaxane conversions. This novel approach could serve to assemble other libraries of small ring molecules, create cyclic polymers bridged by responsive-at-metal nodes, and produce processable mechanically interlocked molecules.     

Alignment and Dynamic Inversion of Planar Chirality in Pillar[n]arenes

Pillar[n]arenes are symmetrical macrocyclic compounds composed of benzene panels with para-methylene linkages. Each panel usually exhibits planar chirality and prefers chirality-aligned states. Because of this feature, pillar[n]arenes are attractive scaffolds for chiroptical materials that are easy to prepare and optically resolve and show intense circular dichroism (CD) signals. In addition, rotation of the panels endows the chirality of pillar[n]arenes with a dynamic nature. The chirality in tubular oligomers and supramolecular assemblies sometimes show time- and procedure-dependent alignment phenomena. Furthermore, the CD signals of some pillar[n]arenes respond to the addition of chiral guests when their dynamic chirality is coupled with host–guest properties. By using diastereomeric pillar[n]arenes with additional chiral structures, the response can also be caused by achiral guests and changes of the environment, providing molecular sensors.     

Synthesis,Characterization, and Computational Investigation of Bright Orange-Emitting Benzothiadiazole [10]Cycloparaphenylene

Conjugated aromatic macrocycles are attractive due to their unique photophysical and optoelectronic properties. In particular, the cyclic radially oriented π-system of cycloparaphenylenes (CPPs) gives rise to photophysical properties unlike any other small molecule or carbon nanomaterial. CPPs have tunable emission, possess large extinction coefficients, wide effective Stokes shifts, and high quantum yields. However, accessing bright CPPs with emissions beyond 500 nm remains difficult. Herein, we present a novel and bright orange-emitting CPP-based fluorophore showing a dramatic 105 nm red-shift in emission and striking 237 nm effective Stokes shift while retaining a large quantum yield of 0.59. We postulate, and experimentally and theoretically support, that the quantum yield remains large due to the lack of intramolecular charge transfer.     

Flow‐Assisted Synthesis of [10]Cycloparaphenylene through Serial Microreactions under Mild Conditions

Cycloparaphenylene (CPP) has been recognized as an attractive template for the bottom‐up synthesis of carbon nanotubes with uniform diameter, and is important for the chemistry of graphitic as well as ring‐shaped macromolecules. However, the reported routes from halogenated benzenes have suffered from low yields even under time‐ and labor‐consuming multistep conditions. Herein we report a flow‐assisted synthesis of [10]CPP in four steps under mild conditions. For the synthesis, a selective nucleophilic addition of the unprotected diketone without the double‐added byproduct was achieved within 3 s in high yield. Subsequently, the obtained compound was reacted with dilithiated benzene at 25 °C to form a U‐shaped precursor for CPP in a separate microreactor, which was finally dimerized and aromatized to obtain [10]CPP by a two‐step in‐flask reaction. Precise control of time and flow facilitated by the flow‐assisted system enabled the development of an efficient synthetic route for [10]CPP.     

A Long‐Lived Azafullerenyl Radical Stabilized by Supramolecular Shielding with a [10]Cycloparaphenylene

A major handicap towards the exploitation of radicals is their inherent instability. In the paramagnetic azafullerenyl radical C₅₉N^., the unpaired electron is strongly localized next to the nitrogen atom, which induces dimerization to diamagnetic bis(azafullerene), (C₅₉N)₂. Conventional stabilization by introducing steric hindrance around the radical is inapplicable here because of the concave fullerene geometry. Instead, we developed an innovative radical shielding approach based on supramolecular complexation, exploiting the protection offered by a [10]cycloparaphenylene ([10]CPP) nanobelt encircling the C₅₉N^. radical. Photoinduced radical generation is increased by a factor of 300. The EPR signal showing characteristic ¹⁴N hyperfine splitting of C₅₉N^.? [10]CPP was traced even after several weeks, which corresponds to a lifetime increase of >10⁸. The proposed approach can be generalized by tuning the diameter of the employed nanobelts, opening new avenues for the design and exploitation of radical fullerenes.     

Dynamic-to-Static Planar Chirality Conversion in Pillar[5]arenes Regulated by Guest Solvents or Amplified by Crystallization

Controlling dynamic chirality and memorizing the controlled chirality are important. Chirality memory has mainly been achieved using noncovalent interactions. However, in many cases, the memorized chirality arising from noncovalent interactions is erased by changing the conditions such as the solvent and temperature. In this study, the dynamic planar chirality of pillar[5]arenes was successfully converted into static planar chirality by introducing bulky groups through covalent bonds. Before introducing the bulky groups, pillar[5]arene with stereogenic carbon atoms at both rims existed as a pair of diastereomers, and thus showed planar chiral inversion that was dependent on the chain length of the guest solvent. The pS and pR forms, regulated by guest solvents, were both diastereomerically memorized by introducing bulky groups. Furthermore, the diastereomeric excess was amplified by crystallization of the pillar[5]arene. The subsequent introduction of bulky groups yielded pillar[5]arene with an excellent diastereomeric excess (95 % de).     

Metal-free synthesis of azacalix[4]arenes

The facile preparation of N(H)-bridged azacalix[4]arenes has been achieved by stepwise nucleophilic aromatic substitutions assisted by hydrogen bonding interactions. The synthesis is uncatalyzed and affords previously unknown tetranitroazacalix[4]arenes.     

Toward Zigzag-edged Helical Nanographene Based on [7]Helicene

Due to their unique chemical and physical properties, zigzag-edged nanographenes have attracted increasing interest in recent years. Herein, a novel zigzag-edged nanographene ( 6 ) containing a [7]helicene subunit was designed and synthesized. However, because of the high reactivities of zigzag edges, compound 1 with a diketone structure was obtained owing to the oxidation of 6 . The helical carbon skeleton of 1 is unambiguously revealed by single-crystal X-ray crystallography analysis. The photophysical properties of the precursor and helical diketone 1 are studied by UV-vis absorption spectroscopy. The electrochemical property of 1 is investigated by cyclic voltammetry, which was further studied by density functional theory (DFT) calculations (ΔE_g^Cal=2.94 eV). The work reported here not only represents the synthesis of an unprecedented [7]helicene-embedded nanographene, but also provides the possibility for the synthesis of helical nanographenes with rich zigzag edges.     

Synthesis,Characterization, and Computational Investigation of Bright Orange‐Emitting Benzothiadiazole [10]Cycloparaphenylene

Conjugated aromatic macrocycles are attractive due to their unique photophysical and optoelectronic properties. In particular, the cyclic radially oriented π‐system of cycloparaphenylenes (CPPs) gives rise to photophysical properties unlike any other small molecule or carbon nanomaterial. CPPs have tunable emission, possess large extinction coefficients, wide effective Stokes shifts, and high quantum yields. However, accessing bright CPPs with emissions beyond 500 nm remains difficult. Herein, we present a novel and bright orange‐emitting CPP‐based fluorophore showing a dramatic 105 nm red‐shift in emission and striking 237 nm effective Stokes shift while retaining a large quantum yield of 0.59. We postulate, and experimentally and theoretically support, that the quantum yield remains large due to the lack of intramolecular charge transfer.     

Building blocks for phospha[n]pericyclynes

Reaction of i-Pr₂NPCl₂ with acetylenic Grignard reagents resulted in the formation of new acetylenic substituted phosphorus building blocks. These building blocks can be protected by forming the corresponding W(CO)₅ complex and the O and S derivatives for added stability as was demonstrated for aminophosphine (11a). From this building block, very sensitive product mixtures containing tetraphospha[4]pericyclynes (16) were obtained. In addition, the amino-substituent of phosphines (11) could be removed upon treatment with HCl to give chlorophosphine (18) from which novel trisethynylphosphines (19) bearing different substituted alkynes were obtained that may serve as building blocks for novel three-dimensional phospha-acetylenic scaffolds such as the (di)ethynyl-expanded phosphacubanes 8 and 25 that, according to DFT calculations, have a higher degree of cyclic electron delocalization and reduced HOMO-LUMO gaps compared to their carbon-analogues.     

Synthesis of upper rim calix[4]arene carcerands

The synthesis of novel tetra-olefinic calix[4]arene carcerands is described using a synthetic strategy involving palladium catalysed Heck coupling followed by imine formation.     

Chiral Calix[3]pyrrole Derivatives: Synthesis,Racemization Kinetics,and Ring Expansion to Calix[9]- and Calix[12]pyrrole Analogues

Chiral pyrrolic macrocycles continue to attract interest. However, their molecular design remains challenging. Here, we report a calixpyrrole-based chiral macrocyclic system, calix[1]furan[1]pyrrole[1]thiophene ( 1 ), synthesized from an oligoketone. Macrocycle 1 adopts a partial cone conformation in the solid state, and undergoes racemization via ring inversion. Molecular dynamics simulations revealed that inversion of the thiophene is the rate determining step. Pyrrole N-methylation suppressed racemization and permitted chiral resolution. Enantioselective N-methylation also occurred in the presence of a chiral ammonium salt, although the stereoselectivity is modest. A unique feature of 1 is that it acts as a useful synthetic precursor to yield several calix[n]furan[n]pyrrole[n]thiophene products (n=2–4), including a calix[12]pyrrole analogue that to our knowledge constitutes the largest calix[n]pyrrole-like species to be structurally characterized.     

Synthetic Modulation of an Unstable Dehydrosecodine-type Intermediate and Its Encapsulation into a Confined Cavity Enable Its X-ray Crystallographic Observation

Numerous indole alkaloids such as the iboga- and aspidosperma-type are believed to be biosynthesized via a common hypothetical intermediate, dehydrosecodine. The highly reactive nature of dehydrosecodine-type compounds has hampered their isolation and structural elucidation. In this study, we achieved the first X-ray structural determination of a dehydrosecodine-type compound by integrating synthetic optimization of the reactivity and stabilizing the fragile molecule by encapsulation into a supramolecular host. Formation of a 1 : 1 complex of the dehydrosecodine-type labile guest bearing both vinyl indole and dihydropyridine units with the host was observed. This integrated approach not only provides insights into the biosynthetic conversions but also allows stabilization and storage of the reactive and otherwise short-lived intermediate within the confined hydrophobic cavity.