Dibenzofuran Moieties Research Articles

Conformationally constrained cyclic grafted peptidomimetics targeting protein-protein interactions.

Sunflower trypsin inhibitor-1 (SFTI-1) structure is used for designing grafted peptides as a possible therapeutic agent. The grafted peptide exhibits multiple conformations in solution due to the presence of proline in the structure of the peptide. To lock the grafted peptide into a major conformation in solution, a dibenzofuran moiety (DBF) was incorporated in the peptide backbone structure, replacing the Pro-Pro sequence. NMR studies indicated a major conformation of the grafted peptide in solution. Detailed structural studies suggested that SFTI-DBF adopts a twisted beta-strand structure in solution. The surface plasmon resonance analysis showed that SFTI-DBF binds to CD58 protein. A model for the protein-SFTI-DBF complex was proposed based on docking studies. These studies suggested that SFTI-1 grafted peptide can be used to design stable peptides for therapeutic purposes by grafting organic functional groups and amino acids. However, when a similar strategy was used with another grafted peptide, the resulting peptide did not produce a single major conformation, and its biological activity was lost. Thus, conformational constraints depend on the sequence of amino acids used for SFTI-1 grafting.

Employing comparative QSAR techniques for the recognition of dibenzofuran and dibenzothiophene derivatives toward MMP-12 inhibition

Among various matrix metalloproteinases (MMPs), MMP-12 is one of the potential targets for cancer and other diseases. However, none of the MMP-12 inhibitors has passed the clinical trials to date. Therefore, designing potential MMP-12 inhibitors as new drug molecules can provide effective therapeutic strategies for several diseases. In this study, a series of dibenzofuran and dibenzothiophene derivatives were subjected to different 2D and 3D-QSAR techniques to point out the crucial structural contributions highly influential toward the MMP-12 inhibitory activity. These techniques identified some structural attributes of these compounds that are responsible for influencing their MMP-12 inhibition. The carboxylic group may enhance proper binding with catalytic Zn2+ ion at the MMP-12 active site. Again, the i-propyl sulfonamido carboxylic acid function contributed positively toward MMP-12 inhibition. Moreover, the dibenzofuran moiety conferred stable binding at the S1′ pocket for higher MMP-12 inhibition. The steric and hydrophobic groups were found favourable near the furan ring substituted at the dibenzofuran moiety. Besides these ligand-based approaches, molecular docking and molecular dynamic (MD) simulation studies not only elucidated the importance of several aspects of these MMP-12 inhibitors while disclosing the significance of the finding of these QSAR studies and their influences toward MMP-12 inhibition. The MD simulation study also revealed stable and compact binding between such compounds at the MMP-12 active site. Therefore, the findings of these validated ligand-based and structure-based molecular modeling studies can aid the development of selective and potent lead molecules that can be used for the treatment of MMP-12-associated diseases. Communicated by Ramaswamy H. Sarma

Anthracene-dibenzofuran based electron transport type hosts for long lifetime multiple resonance pure blue OLEDs

In this work, we report two simple and efficient electron transport (ET) type host materials, namely 2-(3-(10-phenylanthracen-9-yl)-phenyl)dibenzo[b,d]furan (m-PPDF) and 2-(4-(10-phenylanthracen-9-yl)phenyl)dibenzo[b,d]furan (p-PPDF) based on 9,10-diphenylanthracene and dibenzofuran moieties. The designed host materials show excellent thermal stability with thermal decomposition temperature (Td) above 351 °C. The computational studies and carrier transport analysis proved good electron-transporting features of these hosts. The synthesized materials were utilized as hosts for multiple resonance emitters (DABNA-NP-TB) based blue OLEDs. The fabricated OLED device based on p-PPDF host and DABNA-NP-TB dopant shows a high external quantum efficiency (EQE) of 7.03% with a narrow spectrum in deep blue color and Commission International de l’Eclairage (CIE) coordinate of (0.136, 0.076). Further, the operational lifetime at 95% initial luminescence decay (LT 95 ) of the p-PPDF based host device shows 85 h at 600 cd/m 2 , which is increased by 1.7 times compared with the well-known bipolar host (PhPC). Further, we analyzed that such a long lifetime is attributed to the improved stability of electron transfer type-designed hosts. • We report long lifetime fluorescent host materials. • Anthracene-dibenzofuran core host for multi-resonance blue emitter. • EQE of 7.03%, CIE of (0.136, 0.076) and 85h(LT 95 ) at 600nit are reported.

Novel germanium-based σ-π conjugated oligourethanes containing dibenzofuran moieties in the backbone: Thermal, optical, electronic properties and theoretical simulations

In the search of new photoactive materials for light-emitting applications, two new germanium-based oligourethanes (PUGe-27 and PUGe-28) were synthesized from 4,4́-(diphenylgermarylene)bis(phenyl chloroformate) (1) and dibenzo[b,d]furan-2,7-diamine (2) or 4,4′-(dibenzo[b,d]furan-2,8-diyl)dianiline (3) through pyridine-catalysed polycondensation. The structural characterization of the oligourethanes was performed by elemental analysis (EA), IR and NMR techniques. All oligomers were soluble in common organic solvents including THF, which was used to prepare brittle films by casting method. Molecular weights were established in the range of 4.5–5.0 kDa by SEC measures. The samples exhibited a TDT10% in the range of 307–351 °C, while Tg showed values near to 220 °C. Thermal behavior differences were consistent with the molecular flexibility’s degree provided by the monomeric diamine. Suitable absorption and emission behavior were displayed for both germanium-based oligourethanes with moderate Stokes shifts. PUGe-28 showed a strong fluorescence in the blue region of the visible light (364 nm). Both PUGes had wide-band gap (3.76 eV) with interesting high-lying LUMO levels (ac. 2.04 eV). To better understand the experimental results, DFT and TD-DFT calculations were carried out. The results obtained could be used as a guide for future research on Ge-based PUs as photoactive materials.

P‐173: Improved Efficiency in Blue Fluorescent Organic Light‐emitting Devices Using Anthracene‐containing Dibenzofuran‐Type Host Materials

A series of novel blue‐host materials based on anthracene have been synthesized and investigated in which, a π‐electron‐rich dibenzofuran moiety was introduced as a side group to finely adjust the HOMO/LUMO levels of the anthracene and enhance the ability of charge‐transport and injection. To explore the electroluminescent properties of these materials, blue devices of HATCN(30 wt%):BPBPA(40 nm)/BPBPA(10 nm)/PCZAC(10 nm)/Host(30 nm):t‐DABNA(3 wt%)/DBFTrz(5 nm)/ZADN(20 nm)/LiF(1.5 nm)/Al(200 nm) were fabricated. DFAP1 device showed maximum external quantum efficiency of 8.2% with a CIE color coordinate of (0.125, 0.107) and DFAP2 device showed maximum external quantum efficiency of 7.4% with a CIE color coordinate of (0.128, 0.090).

Dibenzofuranylethylamines as 5-HT2A/2C Receptor Agonists.

The human 5-HT2 receptor subtypes have high sequence identity in their orthosteric ligand-binding domain, and many agonists are poorly selective between the 5-HT2A and 5-HT2C subtypes. Nevertheless, their activation is associated with different pharmacological outcomes. We synthesized five phenethylamine analogs in which the benzene ring is replaced by a bulky dibenzo[b,d]furan moiety and found a couple with >70-fold 5-HT2C selectivity. Molecular docking studies of the most potent compound (5) at both receptor subtypes revealed the likely structural basis of its selectivity. Although in both cases, some crucial interactions are conserved, the change of the Ala2225.46 residue in the 5-HT2C receptor to the larger Ser2425.46 in the 5-HT2A subtype, which is the only structural difference between the orthosteric binding pockets of both receptors, weakens a π–π stacking interaction between the dibenzofuran moiety and the important Phe6.52 residue and breaks a hydrogen bond between the dibenzofuran oxygen and Ser5.43, explaining the selectivity of compound 5 for the 5-HT2C receptor. We believe that this effect of the residue at position 5.46 merits further exploration in the search for selective 5-HT2C receptor agonists that are of considerable interest in the treatment of schizophrenia and substance abuse.

Dibenzofuran-based iridium complexes as green emitters: Realizing PhOLEDs with high power efficiency and extremely low efficiency roll-off

In this work, a series of novel iridium (III) cyclometallated complexes BF–Ir1, BF–Ir2 and BF–Ir3 is developed by introducing a dibenzofuran moiety into the main ligand. The photophysical, thermal, and electroluminescent properties of these iridium (III) complexes are systematically investigated. Notably, the phosphorescent organic light-emitting diodes (PhOLEDs) with BF–Ir1, BF–Ir2 and BF–Ir3 as the green emitters displayed the maximum EQEs of 15.1%, 23.7% and 21.5%, respectively. In addition, an impressively high PE up to 96.8 l m W−1 is achieved in the device based on BF–Ir3. When the luminance reached 1000 and 10000 cd m−2, the corresponding EQE values of BF–Ir3-based PhOLEDs could be maintained at 20.7% and 18.5%. These results clearly demonstrate that dibenzofuran-based iridium (III) complexes have great potential for their application as green emitters in PhOLEDs to realize both high EQE and PE as well as low efficiency roll-off.

Achieving Dual‐Emissive and Time‐Dependent Evolutive Organic Afterglow by Bridging Molecules with Weak Intermolecular Hydrogen Bonding

AbstractIt is discovered that “bridging” traditional persistent room‐temperature phosphorescence (pRTP) dibenzofuran moieties by intermolecular hydrogen bonding can induce interesting photophysical properties. The light‐emitting material 4‐(4‐((4‐methoxyphenyl)sulfonyl)phenyl)dibenzo[b,d]furan (SOBF‐OMe) is synthesized and excitingly shows novel dual‐emissive afterglow material properties in which orange pRTP (at ≈580 nm, 627 ms) from the dibenzofuran moiety and another blue ultralong intermolecular charge transfer emission (≈476 nm, 204 ms, with TADF characteristics) can be detected. Due to the different decay lifetimes, the ratio of the two afterglow emission bands continuously changes. Accordingly, the emission colors are unusually tuned gradually from cold‐white to orange during the afterglow decay process. The blue afterglow emission, which relates to intermolecular interactions, is sensitive to mechanical stimuli and the afterglow emission properties of SOBF‐OMe (single‐emissive or dual‐emissive) can easily be manipulated by grinding/fuming. This single‐component material is a rare example of a light‐emitting compound showing dual‐emissive and real‐time changing afterglow properties in which a rational bridging strategy via weak intermolecular hydrogen bonding is utilized.

Synthesis of polyozellin, a prolyl oligopeptidase inhibitor, and its structural revision

Polyozellin is a p-terphenyl compound which was isolated from Polyozellus multiplex, and exhibits an inhibitory activity against prolyl oligopeptidase (POP). Its structure was assigned as 1 having a p-terphenyl skeleton including a p-substituted dibenzofuran moiety by spectroscopic analyses and chemical means. This paper describes the total syntheses of the proposed structure 1 for polyozellin and its o-isomer 2, revising the structure of polyozellin to the latter. These syntheses involved a double Suzuki-Miyaura coupling using chlorophenylboronic acid as a common key building block, and Cu mediated Ullmann cyclization as key steps. The inhibitory activities of synthetic compounds against POP and cancer cells were also evaluated.

New oligomeric poly(ether-imide)s containing diphenylsilane and dibenzofuran moieties. Synthesis and characterization

ABSTRACTA new aromatic diamine, 2,8-di(4-aminophenyl)dibenzofuran, was synthesized through the Suzuki C-C coupling reaction. This compound and an analoge diamine also based on a dibenzofuran moiety reacted with silylated-dianhydrides to yield three aromatic oligomeric poly(ether-imide)s (PEIs). The new diamine and the oligomers were characterized by elemental analysis, FT-IR, and NMR. Additionally, for the samples, solubility in an organic polar solvent was stablished and inherent viscosity values as an indirect measure of the molecular size were recovered. Some properties of PEIs were established and related to the specific structure of the repeating unit. In this sense, the rigidity/flexibility of the main chain fragments and the volume of groups bonded to silicon atom were responsible for the final properties of the polymers. All PEIs were obtained in high yield, but the inherent viscosities values of the soluble samples were low, indicating probably, low to moderated molecular sizes. The thermal decomposition temperatures measured by TGA varied from 490 to 562°C, and the Tg values ranged between 205 and 218°C. The solubility of all samples was tested in a series of common organic solvents at room temperature and at 40°C. The optical transparency in solution for the soluble samples was also determined.

Synthesis of 3-phenyldibenzo[b,d]furan-type bioprobes utilizing vialinin B as a structural motif

ABSTRACTVialinin B is a natural 3-phenyldibenzo[b,d]furan product with a powerful inhibitory activity against tumor necrosis factor (TNF)–α production. This article describes the synthesis of three types of biotinylated p-terphenyls designed for clarifying the target molecule of vialinin B. Construction of the carbon backbone of the core was accomplished by stepwise Suzuki–Miyaura coupling while the phenyl dibenzofuran moiety was built up by the Ullmann reaction. The biotinyl unit was attached through click chemistry.

Syntheses of the Fungal Metabolites Boletopsins 7, 11, and 12 from the Papua New Guinea Medicinal Mushroom Boletopsis sp.

Boletopsins 7 (1), 11 (2), and 12 (3) are p-terphenyl dibenzofuran compounds, isolated from the Papua New Guinean medicinal mushroom Boletopsis sp. The first syntheses of these fungal metabolites are reported, allowing for an investigation of their antibiotic activity. The key steps include sequential Suzuki-Miyaura couplings to rapidly form the p-terphenyl backbone and an Ullmann ether synthesis on a formate ester to create the dibenzofuran moiety. Biological evaluation of the synthetic compounds and intermediates against a panel of bacterial nosocomial pathogens was performed.

Discovery and biological evaluation of novel 1,4-benzoquinone and related resorcinol derivatives that inhibit 5-lipoxygenase

5-Lipoxygenase (5-LO), an enzyme that catalyzes the initial steps in the biosynthesis of pro-inflammatory leukotrienes, is an attractive drug target for the pharmacotherapy of inflammatory and allergic diseases. Here, we present the discovery and biological evaluation of novel series of 1,4-benzoquinones and respective resorcinol derivatives that efficiently inhibit human 5-LO, with little effects on other human lipoxygenases. SAR analysis revealed that the potency of the compounds strongly depends on structural features of the lipophilic residues, where bulky naphthyl or dibenzofuran moieties favor 5-LO inhibition. Among the 1,4-benzoquinones, compound Ig 5-[(2-naphthyl)methyl]-2-hydroxy-2,5-cyclohexadiene-1,4-dione potently blocked 5-LO activity in cell-free assays with IC50 = 0.78 μM, and suppressed 5-LO product synthesis in polymorphonuclear leukocytes with IC50 = 2.3 μM. Molecular docking studies suggest a concrete binding site for Ig in 5-LO where select π–π interactions along with hydrogen bond interactions accomplish binding to the active site of the enzyme. Together, our study reveals novel valuable 5-LO inhibitors with potential for further preclinical assessment as anti-inflammatory compounds.

Elevating the Triplet Energy Levels of Dibenzofuran‐Based Ambipolar Phosphine Oxide Hosts for Ultralow‐Voltage‐Driven Efficient Blue Electrophosphorescence: From DA to DπA Systems

A series of donor (D)-π-acceptor (A)-type phosphine-oxide hosts (DBF(x) POPhCz(n)), which were composed of phenylcarbazole, dibenzofuran (DBF), and diphenylphosphine-oxide (DPPO) moieties, were designed and synthesized. Phenyl π-spacer groups were inserted between the carbazolyl and DBF groups, which effectively weakened the charge transfer and triplet-excited-state extension. As the result, the first triplet energy levels (T(1)) of DBF(x)POPhCz(n) are elevated to about 3.0 eV, 0.1 eV higher than their D-A-type analogues. Nevertheless, the electrochemical analysis and DFT calculations demonstrated the ambipolar characteristics of DBF(x)POPhCz(n). The phenyl π spacers hardly influenced the frontier molecular orbital (FMO) energy levels and the carrier-transporting ability of the materials. Therefore, these D-π-A systems are endowed with higher T(1) states, as well as comparable electrical properties to D-A systems. Phosphorescent blue-light-emitting diodes (PHOLEDs) that were based on DBF(x)POPhCz(n) not only inherited the ultralow driving voltages (2.4 V for onset, about 2.8 V at 200 cd m(-2), and <3.4 V at 1000 cd m(-2)) but also had much-improved efficiencies, including about 26 cd A(-1) for current efficiency, 30 Lm W(-1) for power efficiency, and 13% for external quantum efficiency, which were more than twice the values of devices that are based on conventional unipolar host materials. This performance makes DBFDPOPhCz(n) among the best hosts for ultralow-voltage-driven blue PHOLEDs reported so far.

Synthesis and characterization of aromatic polyamides derived from various derivatives of 4,4’-oxydianiline

Three aromatic diamines, 2,2′-diiodo-4,4′-oxydianiline (DI-ODA 2), 2,2′-bis[p-(trifluoromethyl)phenyl]-4,4′-oxydianiline (BTFP-ODA 3) and 2,8-diaminodibenzofuran (DADBF 5) were synthesized by using 4,4-oxydianiline (4,4′-ODA) as the starting material. New aromatic polyamides 6, 7 and 8 were prepared from these three diamines and six commercially available aromatic diacids by direct polycondensation, respectively. Polyamides 6 and 7 contained bulky iodide and p-trifluoromethylphenyl substitutents that would hinder the chain packing and increase the free volume. They exhibited good optical transparency in visible light region and showed excellent solubility in organic solvents such as DMSO, DMAc, DMF and NMP. Polyamides 8 containing planar dibenzofuran moieties had the highest glass transition temperatures and decomposition temperatures among these polyamides. Polyamides 6 had the lowest decomposition temperatures due to the presence of weak carbon–iodine bond. All of these polyamides showed amorphous nature evidenced by wide angle X-ray diffraction. No endothermic peaks were observed from DSC thermograms up to their decomposition temperatures. High optical transparency and excellent solubility combined with good thermal stability make these polyamides attractive for potential soft electronics applications.

Thermal decomposition products of copoly(arylene ether sulfone)s characterized by direct pyrolysis mass spectrometry

Pyrolysis products with mass of up to 850 Da were detected by direct pyrolysis mass spectrometric (DPMS) analysis of a series of copoly(arylene ether sulfone)s (PES–PPO) synthesized by nucleophilic condensation of either 4,4′-dichlorodiphenylsulfone (CDPS) or 4,4′-bis-(4-chlorophenyl sulfonyl) biphenyl (long chain dichloride, LCDC) with different molar ratios of hydroquinone (HQ) or dihydroxydiphenylsulfone (HDPS). Pyrolysis products retaining the repeating units of the initial copolymers were formed at temperatures ranging from 420 °C to 470 °C (near the initial decomposition temperature). At temperatures higher than 450 °C were observed products containing biphenyl units, formed by the elimination process of SO 2 from diphenyl sulfone bridges. Products having biphenyl and dibenzofuran moieties were detected in the mass spectra recorded at temperatures above 550 °C. These units were formed by loss of hydrogen atom from diphenyl ether bridges. Although the EI (18 eV) mass spectra of the pyrolysis products of the samples investigated were very similar, it was found that the relative intensity of some ions reflects the molar composition of the copolymers analysed. Cyclic and linear oligomers with very low molecular mass, present in the crude copolymers, were also detected by DPMS. Thermogravimetric analysis also showed their excellent thermal stability below 400 °C. It indicates that the copolymers yield a char residue of 40–45% at 800 °C, which increases with the PPO mole fraction in the samples.

Quantum Chemical Study of Low Temperature Oxidation Mechanism of Dibenzofuran

A density functional theory (DFT) study of the reaction of dibenzofuranyl radical with oxygen molecule has been made. The geometries, energies, and vibrational frequencies of the reactant, transition states, intermediates, and products have been calculated at the B3LYP/6-311+G(3df,2p)//B3LYP/6-31G(d) level of theory. The initial reaction of dibenzofuran (DBF) with molecular oxygen results in the formation of the 1-dibenzofuranylperoxy radical. The stability of this adduct toward decomposition at low to intermediate temperatures results in it undergoing several possible rearrangements. The lowest energy pathway with a barrier of 24.2 kcal/mol involves a rearrangement to the 1,1-dioxadibenzofuran radical. The next lowest energy pathway involves fission of the O-O linkage whose reaction energy was found to be 37.6 kcal/mol. Transition state theory (TST) calculations indicate that the lowest energy pathway should predominate at temperatures up to about 1200 K. Two other unimolecular reaction pathways with barriers of 45.5 and 91.1 kcal/mol have also been discovered. The latter pathway leads to the formation of a para-quinone (dibenzofuran quinone) which has been detected experimentally in the low-temperature oxidation of DBF [Marquaire, P. M.; Worner, R.; Rambaud, P.; Baronnet, F. Organohalogen Compd. 1999, 40, 519]. Our quantum calculations, however, do not support this latter pathway to quinone formation. Instead, the quinone is most probably formed as a consequence of recombination of the 1-dibenzofuranyloxy radical (produced by peroxy fission) with an O atom in the para position. Each of the unimolecular reaction pathways have been subjected to detailed quantum chemical investigation and transition states and intermediates leading to the final products (principally CO, CO2, and C2H2 with traces of benzofuran and benzene) have been identified. For certain stable intermediates, their possible reactions with molecular oxygen have been further investigated quantum chemically. The present work therefore presents a detailed quantum chemical investigation of the reaction pathways in the low-temperature oxidation mechanism of DBF. Since the dibenzofuran moiety is present in the polychlorinated DBFs, our conclusions should be generally applicable to this family of compounds.

Synthesis and Cytotoxicity Evaluation of Certain -Methylidene- -butyrolactones Bearing Coumarin, Flavone, Xanthone, Carbazole, and Dibenzofuran Moieties

The cytotoxicities of α-methylidene-γ-butyrolactones, which are linked to coumarins (see 15 and 16) and to potential DNA-intercalating carriers such as flavones, xanthones, carbazole, and dibenzofuran (see 9a – e, 10a – e, 11, and 12), were studied. These compounds were synthesized via alkylation of their hydroxy precursors followed by a Reformatsky-type condensation (Scheme). These α-methylidene-γ-butyralactones were evaluated in vitro against 60 human tumor cell lines derived from nine cancer cell types and demonstrated a strong growth-inhibitory activity against leukemia cancer cells (Tables 1 and 2). For flavone- and xanthone-containing α-methylidene-γ-butyrolactones 9a – e and 10a – e, respectively, the overall potency (mean value) decreased on introduction of an electron-withdrawing substituent at the γ-phenyl substituent and increased with an electron-donating substituent. Comparing the different chromophores established the following order of decreasing potency (log GI50): dibenzofuran (12, −6.17) > flavone (9a, −5.96) > carbazole (11, −5.80) and xanthone (10a, −5.77) > coumarin (15, −5.60; 16, −5.65). Among them, the dibenzofuran derivative 12 showed not only strong inhibitory activities against leukemia cancer cell lines with an average log GI50 value of −7.22, but also good inhibitory activities against colon, melanoma, and breast cancer cells with average log GI50 values of −6.23, −6.31, and −6.39, respectively.

Synthesis and use of water-soluble sulfonated dibenzofuran-based phosphine ligands

The syntheses of three triphenylphosphine analogues with one, two or three phenyl groups replaced by 2-dibenzofuranyl groups, respectively, and one enantiopure analogue of the atropisomeric diphosphine MeO-BIPHEP with all four phenyl groups replaced by 2-dibenzofuranyl are reported. Sulfonation of these compounds with sulfuric acid at rt proceeded with complete regioselectivity at the 8-position in the dibenzofuran moieties. These results proved the usefulness of dibenzofuran as a structural moiety in the synthesis of water-soluble phosphine ligands. The dibenzofuran-based, water-soluble triphenylphosphine analogues were used as ligands in palladium-catalysed aqueous phase Heck and Suzuki reactions and in the rhodium-catalysed two-phase hydroformylation of propene.

Molecular and Supramolecular Synthesis with Dibenzofuran‐Containing Systems

AbstractThe template‐directed syntheses of two new tetracationic cyclophanes, cyclobis(paraquat‐2,8‐dibenzofuran) and cyclobis(paraquat‐3,7‐dibenzofuran), incorporating dibenzofuran subunits has been accomplished. Initially, the cyclophanes were self‐assembled around a macrocyclic polyether template, bis‐p‐phenylene[34]crown‐10 (BPP34C10), to form catenanes: the mechanical bond order of the catenane formed determined the requisite “amacrocyclic” templates for synthesis of the free cyclophane. X‐ray crystallography shows that both of the cyclophanes possess rectangular covalent frameworks. Furthermore, these cyclophanes form self‐assembled tapes in the solid state, since the dibenzofuran moieties have a tendency to associate with each other through crossed ∞–∞ stacks. The dibenzofuran‐containing catenanes also form two‐dimensional supramolecular arrays in the solid state on account of extended ∞–∞ stacking interactions. In addition, the serendipitous discovery of a plerotopic tecton (consisting of a dibenzofuran nucleus covalently linked from the 2‐ and 8‐positions by methylene groups to 4,4′‐pyridylpyridinium (hydrogen bond acceptor) and protonated bipyridinium (hydrogen bond donor) units) has been made. The tecton dimerizes in the solid state to form a supramolecular macrocycle, since its complementary hydrogen bonding sites are oriented in a horseshoelike fashion by the 2,8‐disubstituted dibenzofuran unit. However, this superstructure is not retained in the 1:1 complex of the tecton with BPP34C10: cocrystallization of the tecton with this crown ether opens the macrocyclic two‐component supermolecule to afford a hydrogen‐bonded pseudopolyrotaxane.