Tetracationic Cyclophane Research Articles

Solvent-induced modulation of sensitivity and selectivity in the self-assembly of tetracationic cyclophanes with cholesterol sulphate, sodium dodecyl sulfate, and sodium dodecyl benzene sulfonate: Observations of significant shifts

Cyclophane CP-1 demonstrates markedly distinct sensitivities toward Cholesterol sulfate (CH-S), Sodium Dodecyl Sulfate (SDS), and Sodium Dodecyl Benzene Sulfonate (SDBS) when the solvent is shifted minimally from a 95 % to a 98 % HEPES-DMSO mixture. In a 98:2 HEPES-DMSO mixture, CP-1 engages in highly selective self-assembly with CH-S, which is characterized by aggregation-induced emission enhancement (AIEE) in contrast to other steroidal sulfates such as pregnenolone sulfate (PRG-S), dehydroisoandrosterone sulfate (DIAND-S), taurocholic acid (TACH-S), and the surfactants SDS and SDBS. This assembly results in an approximate 40-fold increase in fluorescence intensity with three equivalents of CH-S and allows for the detection of concentrations as low as 200 nM under physiological conditions. Dynamic light scattering (DLS) studies illustrate the aggregation of CP-1 and CH-S, with the zeta potential of each shifting from negative values to nearly zero in a 1:2 CP-1:CH-S mixture, indicating self-assembly. This aggregation behavior is reversible, as demonstrated by a corresponding decrease and then increase in fluorescence intensity with temperature variations from 25 °C to 70 °C and back to 25 °C. Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM) analyses show that CP-1 forms aggregates ranging from 100 to 180 nm, which increase to 150–250 nm upon interaction with CH-S. In a 95:5 HEPES-DMSO mixture, CP-1 exhibits a stronger AIEE response with SDS and SDBS compared to CH-S. Cyclophane CP-2, when dissolved in binary DMSO-water mixtures with water content exceeding 80 %, shows similar AIEE phenomena and undergoes selective fluorescence quenching with SDS and only a 50 % increase in fluorescence intensity with CH-S, irrespective of the HEPES concentration (95 % or 98 %).

Directional Electron Flow in a Selenoviologen-Based Tetracationic Cyclophane for Enhanced Visible-Light-Driven Hydrogen Evolution.

Directional electron flow in the photocatalyst enables efficient charge separation, which is essential for efficient photocatalysis of H2 production. Here, we report a novel class of tetracationic cyclophanes (7) incorporating bipyridine Pt(II) and selenoviologen. X-ray single-crystal structures reveal that 7 not only fixes the distances and spatial positions between its individual units but also exhibits a box-like rigid electron-deficient cavity. Moreover, host-guest recognition phenomena are observed between 7 and ferrocene, forming host-guest complexes with a 1:1stoichiometryin MeCN. 7exhibits good redox properties, narrow energy gaps, and strong absorption in the visible range (370-500 nm) due to containing two selenoviologen(SeV2+)units.Meanwhile, the femtosecond transient absorption (fs-TA) reveals that 7 has stabilized dicationic biradical, efficient charge separation, and facilitates directional electron flow to achieve efficient electron transfer due to the formation of rigid cyclophane and electronic architecture. Then, 7 is applied to visible-light-driven hydrogen evolution with high hydrogen production (132 μmol), generation rate (11 μmol/h),turnover number (221), and apparent quantum yield (1.7%), which provides a simplified and efficient photocatalytic strategy for solar energy conversion.

Directional Electron Flow in a Selenoviologen‐Based Tetracationic Cyclophane for Enhanced Visible‐Light‐Driven Hydrogen Evolution

Directional electron flow in the photocatalyst enables efficient charge separation, which is essential for efficient photocatalysis of H2 production. Here, we report a novel class of tetracationic cyclophanes (7) incorporating bipyridine Pt(II) and selenoviologen. X‐ray single‐crystal structures reveal that 7 not only fixes the distances and spatial positions between its individual units but also exhibits a box‐like rigid electron‐deficient cavity. Moreover, host‐guest recognition phenomena are observed between 7 and ferrocene, forming host‐guest complexes with a 1:1 stoichiometry in MeCN. 7 exhibits good redox properties, narrow energy gaps, and strong absorption in the visible range (370‐500 nm) due to containing two selenoviologen (SeV2+) units. Meanwhile, the femtosecond transient absorption (fs‐TA) reveals that 7 has stabilized dicationic biradical, efficient charge separation, and facilitates directional electron flow to achieve efficient electron transfer due to the formation of rigid cyclophane and electronic architecture. Then, 7 is applied to visible‐light‐driven hydrogen evolution with high hydrogen production (132 μmol), generation rate (11 μmol/h), turnover number (221), and apparent quantum yield (1.7%), which provides a simplified and efficient photocatalytic strategy for solar energy conversion.

The paradigm for exceptional iodine capture by nonporous amorphous electron-deficient cyclophanes

Nuclear power emerges as a beacon of hope in tackling the energy crisis. However, the emission of radioactive iodine originating from nuclear waste and accidents poses a serious danger to nature and human well-being. Therefore, it becomes imperative to urgently develop suitable adsorbents capable of iodine capture and long-term storage. It’s generally recognized that achieving high iodine capture efficiency necessitates the presence of electron-rich pores/cavities that facilitate charge-transfer (CT) interactions, as well as effective sorption sites capable of engaging in lone pair interactions with iodine. In this study, an unprecedented iodine capture paradigm by nonporous amorphous electron-deficient tetracationic cycloalkanes in vapor and aqueous solutions is revealed, overturning preconceived notions of iodine trapping materials. A newly reported tetracationic cyclophane, BPy-Box4+, exhibited an exceptional iodine vapor sorption capacity of 3.99 g g−1, remarkable iodine removal efficiency in aqueous media, and outstanding reusability. The iodine capture mechanism is unambiguously elucidated by theoretical calculations and the single-crystal structures of cyclophanes with a gradual increase in iodine content, underlining the vital role of host-guest (1:1 or 1:2) interactions for the enhanced iodine capture. The current study demonstrates a new paradigm for enhanced iodine capture by nonporous amorphous electron-deficient cyclophanes through host-guest complexation.

Quantum Sensing of Electric Fields Using Spin-Correlated Radical Ion Pairs.

Quantum sensing affords the possibility of using quantum entanglement to probe electromagnetic fields with exquisite sensitivity. In this work, we show that a photogenerated spin-correlated radical ion pair (SCRP) can be used to sense an electric field change created at one radical ion of the pair using molecular recognition. The SCRP is generated within a covalent donor-chromophore-acceptor system PXX-PMI-NDI, 1, where PXX = peri-xanthenoxanthene, PMI = 1,6-bis(p-t-butylphenoxy)perylene-3,4-dicarboximide, and NDI = naphthalene-1,8:4,5-bis(dicarboximide). The electron-rich PXX donor in 1 acts as a guest molecule that can be encapsulated selectively by a tetracationic cyclophane ExBox4+ host to give a supramolecular complex 1 ⊂ ExBox4+. Selective photoexcitation of the PMI chromophore results in ultrafast generation of the PXX•+-PMI-NDI•- SCRP. When PXX is encapsulated by ExBox4+, the cyclophane generates an electric field that repels the positive charge on PXX•+ within PXX•+-PMI-NDI•-, reducing the SCRP distance, i.e., the distance between the centers-of-charge on the donor and acceptor. Pulse-EPR measurements are used to measure the coherent oscillations created primarily by the electron-electron dipolar coupling in the SCRP, which yields the distance between the two charges (spins) of PXX•+-PMI-NDI•-. The experimental results show that the distance between PXX•+ and NDI•- decreases when ExBox4+ encapsulates PXX•+, which demonstrates that the SCRP can function as a quantum sensor to detect electric field changes in the vicinity of the radical ions.

Divinylanthracene-Containing Tetracationic Organic Cyclophane with Near-Infrared Photoluminescence

Near-infrared (NIR) light is known to have outstanding optical penetration in biological tissues and to be non-invasive to cells compared with visible light. These characteristics make NIR-specific light optimal for numerous biological applications, such as the sensing of biomolecules or in theranostics. Over the years, significant progress has been achieved in the synthesis of fluorescent cyclophanes for sensing, bioimaging, and making optoelectronic materials. The preparation of NIR-emissive porphyrin-free cyclophanes is, however, still challenging. In an attempt for fluorescence emissions to reach into the NIR spectral region, employing organic tetracationic cyclophanes, we have inserted two 9,10-divinylanthracene units between two of the pyridinium units in cyclobis(paraquat-p-phenylene). Steady-state absorption, fluorescence, and transient-absorption spectroscopies reveal the deep-red and NIR photoluminescence of this cyclophane. This tetracationic cyclophane is highly soluble in water and has been employed successfully as a probe for live-cell imaging in a breast cancer cell line (MCF-7).

The Green Box: Selenoviologen-Based Tetracationic Cyclophane for Electrochromism, Host–Guest Interactions, and Visible-Light Photocatalysis

The novel selenoviologen-based tetracationic cyclophanes (green boxes 3 and 5) with rigid electron-deficient cavities are synthesized via SN2 reactions in two steps. The green boxes exhibit good redox properties, narrow energy gaps, and strong absorption in the visible range (370-470 nm), especially for the green box 5 containing two selenoviologen (SeV2+) units. Meanwhile, the femtosecond transient absorption (fs-TA) reveals that the green boxes have a stabilized dicationic biradical, high efficiency of intramolecular charge transfer (ICT), and long-lived charge separation state due to the formation of cyclophane structure. Based on the excellent photophysical and redox properties, the green boxes are applied to electrochromic devices (ECDs) and visible-light-driven hydrogen production with a high H2 generation rate (34 μmol/h), turnover number (203), and apparent quantum yield (5.33 × 10-2). In addition, the host-guest recognitions are demonstrated between the green boxes and electron-rich guests (e.g., G1:1-naphthol and G2:platinum(II)-tethered naphthalene) in MeCN through C-H···π and π···π interactions. As a one-component system, the host-guest complexes of green box⊃G2 are successfully applied to visible-light photocatalytic hydrogen production due to the intramolecular electron transfer (IET) between platinum(II) of G2 and SeV2+ of the green box, which provides a simplified system for solar energy conversion.

Cucurbit[10]uril-based supramolecular radicals: Powerful arms to kill facultative anaerobic bacteria.

Two water-soluble supramolecular complexes (CB[10]⊃PSA and CB[10]⊃TPE-cyc) are constructed based on the host-guest interaction between cucurbit[10]uril (CB[10]) and perylene diimide derivative (PSA) or tetracationic cyclophane (TPE-cyc). Attributing to the matched redox potential, both supramolecular complexes can be specifically reduced into corresponding supramolecular radical cations or anions by facultative anaerobic E. coli. Benefiting from the strong near-infrared (NIR) absorption, CB[10]⊃PSA radical anions and CB[10]⊃TPE-cyc radical cations act as efficient NIR photosensitizers and perform an excellent antimicrobial activity (close to 100%) via PTT. In addition, the biocompatibility of TPE-cyc is notably improved under the protection of CB[10], guaranteeing its biosafety for in vivo application. CB[10]⊃PSA radical anions and CB[10]⊃TPE-cyc radical cations are in situ generated in the E. coli-infected abscess of mice and effectively inhibit the bacterial infection without obvious system toxicity. It is anticipated that this supramolecular strategy may pave a new way for the selective bacteria inhibition to regulate the balance of different bacterial flora.

Host-guest binding of tetracationic cyclophanes to photodynamic agents inhibits posttreatment phototoxicity and maintains antitumour efficacy.

In the past two decades, photodynamic therapy (PDT) has become an effective method for the treatment of cancer. However, the posttreatment residue of photodynamic agents (PDAs) causes long-term skin phototoxicity. Here, we apply naphthalene-derived, box-like tetracationic cyclophanes, named NpBoxes, to bind to clinically used porphyrin-based PDAs to alleviate their posttreatment phototoxicity by reducing their free content in skin tissues and 1O2 quantum yield. We show that one of the cyclophanes, 2,6-NpBox, could include the PDAs to efficiently suppress their photosensitivity for the generation of reactive oxygen species. A tumour-bearing mouse model study revealed that, when Photofrin, the most widely used PDA in clinic, was administrated at a dose corresponding to the clinical one, 2,6-NpBox of the same dose could significantly suppress its posttreatment phototoxicity on the skin induced by simulated sunlight irradiation, without imposing a negative influence on its PDT efficacy.

Thermoresponsive catechol end‐functionalized polymers/CBPQT4+, 4Cl− supramolecular assembly

AbstractIn the past decade, the adhesive properties of catechol derivatives have inspired researchers for the design of various macromolecular architectures featuring fascinating properties and finding applications in energy storage, coatings, adhesives and biomaterials. In this work, the complexation of catechol end‐functionalized polymers prepared by RAFT polymerization was investigated in aqueous media with the electron‐deficient tetracationic cyclophane cyclobis(paraquat‐p‐phenylene) (CBPQT4+) by using UV–Vis and 1H NMR experiments. The formation of pseudorotaxanes between the catechol end‐functionalized polymers and the CBPQT4+,4Cl− leads to the formation of colored guest‐specific complexes displaying tunable complexation properties. In particular, we demonstrated that the thermo‐responsiveness i.e. the lower critical solution temperature (LCST) of the catechol end‐functionalized poly(NIPAM) could be used as a simple and convenient tool to disrupt the complexation with CBPQT4+; 4Cl− resulting in the disappearance of the characteristic color of the Catechol/BB complex while releasing the cyclophane in the aqueous solution. Furthermore, these supramolecular host/guest assemblies could be disrupted, on demand, by the addition of a competitive Naphthalene derivative leading to the appearance of the characteristic purple color of Naphthalene/CBPQT4+ complexes. These results pave the way for the design of a new generation of stimuli responsive materials with control properties.

The Story of the Little Blue Box: A Tribute to Siegfried Hünig.

The tetracationic cyclophane, cyclobis(paraquat-p-phenylene), also known as the little blue box, constitutes a modular receptor that has facilitated the discovery of many host-guest complexes and mechanically interlocked molecules during the past 35 years. Its versatility in binding small π-donors in its tetracationic state, as well as forming trisradical tricationic complexes with viologen radical cations in its doubly reduced bisradical dicationic state, renders it valuable for the construction of various stimuli-responsive materials. Since the first reports in 1988, the little blue box has been featured in over 500 publications in the literature. All this research activity would not have been possible without the seminal contributions carried out by Siegfried Hünig, who not only pioneered the syntheses of viologen-containing cyclophanes, but also revealed their rich redox chemistry in addition to their ability to undergo intramolecular π-dimerization. This Review describes how his pioneering research led to the design and synthesis of the little blue box, and how this redox-active host evolved into the key component of molecular shuttles, switches, and machines.

The Story of the Little Blue Box: A Tribute to Siegfried Hünig

AbstractThe tetracationic cyclophane, cyclobis(paraquat‐p‐phenylene), also known as the little blue box, constitutes a modular receptor that has facilitated the discovery of many host–guest complexes and mechanically interlocked molecules during the past 35 years. Its versatility in binding small π‐donors in its tetracationic state, as well as forming trisradical tricationic complexes with viologen radical cations in its doubly reduced bisradical dicationic state, renders it valuable for the construction of various stimuli‐responsive materials. Since the first reports in 1988, the little blue box has been featured in over 500 publications in the literature. All this research activity would not have been possible without the seminal contributions carried out by Siegfried Hünig, who not only pioneered the syntheses of viologen‐containing cyclophanes, but also revealed their rich redox chemistry in addition to their ability to undergo intramolecular π‐dimerization. This Review describes how his pioneering research led to the design and synthesis of the little blue box, and how this redox‐active host evolved into the key component of molecular shuttles, switches, and machines.

Alkoxy-Substituted Quadrupolar Fluorescent Dyes.

Polar and polarizable π-conjugated organic molecules containing push-pull chromophores have been investigated extensively in the past. Identifying unique backbones and building blocks for fluorescent dyes is a timely exercise. Here, we report the synthesis and characterization of a series of fluorescent dyes containing quadrupolar A-D-A constitutions (where A = acceptor and D = donor), which exhibit fluorescence emission at a variety of different wavelengths. We have investigated the effects of different electron-withdrawing groups, located at both termini of a para-terphenylene backbone, by steady-state UV/vis and fluorescence spectroscopy. Pyridine and substituted pyridinium units are also introduced during the construction of the quadrupolar backbones. Depending on the quadrupolarity, fluorescence emission wavelengths cover from 380 to 557 nm. Time-resolved absorption and emission spectroscopy reveal that the photophysical properties of those quadrupolar dyes result from intramolecular charge transfer. One of the dyes we have investigated is a symmetrical box-like tetracationic cyclophane. Its water-soluble tetrachloride, which is non-cytotoxic to cells up to a loading concentration of 1 μM, has been employed in live-cell imaging. When taken up by cells, the tetrachloride emits a green fluorescence emission without any hint of photobleaching or disruption of normal cell behavior. We envision that our design strategy of modifying molecules through the functionalization of the quadrupolar building blocks as chromophores will lead to future generations of fluorescent dyes in which these A-D-A constitutional fragments are incorporated into more complex molecules and polymers for broader photophysical and biological applications.

Aggregation‐Induced Emission and Circularly Polarized Luminescence Duality in Tetracationic Binaphthyl‐Based Cyclophanes

AbstractHere, we report an approach to the synthesis of highly charged enantiopure cyclophanes by the insertion of axially chiral enantiomeric binaphthyl fluorophores into the constitutions of pyridinium‐based macrocycles. Remarkably, these fluorescent tetracationic cyclophanes exhibit a significant AIE compared to their neutral optically active binaphthyl precursors. A combination of theoretical calculations and time‐resolved spectroscopy reveal that the AIE originates from limited torsional vibrations associated with the axes of chirality present in the chiral enantiomeric binaphthyl units and the fine‐tuning of their electronic landscape when incorporated within the cyclophane structure. Furthermore, these highly charged enantiopure cyclophanes display CPL responses both in solution and in the aggregated state. This unique duality of AIE and CPL in these tetracationic cyclophanes is destined to be of major importance in future development of photonic devices and bio‐applications.

Cyclophane-based two-dimensional polymer formed by an interfacial click reaction

Two-dimensional polymers (2DPs) that incorporate molecular hosts offer a distinctive combination of properties, including covalent connectivity, structural regularity, chemical stability, permanent porosity, and molecular recognition. These features make these topologically planar macromolecular sheets promising in relation to applications, including those that appear in sensors, organic electronics, and nanofiltration membranes. Here, we use copper-catalyzed azide-alkyne click chemistry to construct a cyclophane-based 2DP at a liquid-liquid interface by polymerizing a bisazide-functionalized tetracationic cyclophane monomer with a 1,3,5-triethynylbenzene node. The 2DP prepared by employing this strategy is observed to be crystalline porous sheets by a combination of synchrotron X-ray diffraction, transmission electron microscopy, electron diffraction, and nitrogen porosimetry. When employed as the active layer in nanofiltration membranes, this 2DP exhibits excellent rejection performance of a dye, Brilliant Blue G, with 99% of the dye being removed after each cycle. Our findings could lead to the broad application of interfacial click polymerizations to produce 2DPs.

Fluorescence Quenching by Redox Molecular Pumping

Artificial molecular pumps (AMPs), inspired by the active cellular transport exhibited in biological systems, enable cargoes to undergo unidirectional motion, courtesy of molecular ratchet mechanisms in the presence of energy sources. Significant progress has been achieved, using alternatively radical interactions and Coulombic repulsive forces to create working AMPs. In an attempt to widen the range of these AMPs, we have explored the effect of molecular pumping on the photophysical properties of a collecting chain on a dumbbell incorporating a centrally located pyrene fluorophore and two terminal pumping cassettes. The AMP discussed here sequesters two tetracationic cyclophanes from the solution, generating a [3]rotaxane in which the fluorescence of the dumbbell is quenched. The research reported in this Article demonstrates that the use of pumping cassettes allows us to generate the [3]rotaxane in which the photophysical properties of fluorophores can be modified in a manner that cannot be achieved with a mixture of the dumbbell and ring components of the rotaxane on account of their weak binding in solution.

Hydrophilic Tetraphenylethene-Based Tetracationic Cyclophanes: NADPH Recognition and Cell Imaging With Fluorescent Switch.

A hydrophilic TPE-based tetracationic cyclophane TPE-cyc was synthesized, which could capture intracellular Nicotinamide adenine dinucleotide phosphate and fuel the antioxidative ability of tumor cells to detoxify reactive oxygen species (ROS). Meanwhile, upon the reduction by cellular GSH, TPE-cyc could light up tumor cells, acting as a GSH-responsive fluorescent switch to image cells with high resolution.

Whither Second-Sphere Coordination?

Whither Second-Sphere Coordination?

Cationic cyclophanes-in-cucurbit[10]uril: host-in-host complexes showing cooperative recognition towards neutral phenol guests

ABSTRACT Cucurbit[10]uril (CB[10]) is found to form stable host-guest complexes with tetracationic cyclophanes in H2O and DMSO. Upon encapsulation in CB[10], the affinity of cyclophanes towards anions is weakened, due to electronegative carbonyl oxygens on CB[10] providing charge repulsion environment, and encapsulation fixing the conformation of cyclophanes. Interestingly, these complexes show positively cooperative effects towards neutral phenol guests to form heteroternary complexes. The driving force for the formation of heteroternary inclusion complexes is multiple hydrogen bonding interactions confirmed by X-ray single crystal analysis, as well as hydrophobic effects.

Promotion and suppression of single-molecule conductance by quantum interference in macrocyclic circuits

Promotion and suppression of single-molecule conductance by quantum interference in macrocyclic circuits