1,721,010 research outputs found
Formation of a Pd16 Molecular Basket Architecture of Reduced Symmetry and Angular Deviation in a Fluorenone Scaffold to Govern the Host–Guest Chemistry of Pd6 Trifacial Tubes
No full textThe employment of flexible ligands with significant conformational freedom in coordination-driven self-assembly enables the formation of unique and intricate structures. In this study, the self-assembly of such a fluorenone-appended ligand (L1) with a sterically demanding acceptor, [Pd(tmed)(ONO2)2] (M1), generated a new and unique molecular basket architecture, (M1)16(L1)8 (B), featuring a large hollow cavity. B possesses an unusual twisted architecture of low symmetry, consisting of 16 Pd(II) centers arranged as four tetrahedra connected by eight flexible ligands, representing a structurally complex system reminiscent of biological architectures. Designing such entropically disfavored, large architectures of reduced symmetry is challenging but desirable, since they can act as ideal models to study complicated natural systems. The host–guest property of supramolecular hosts is governed by the confined cavities and noncovalent interactions, which are dictated by the angular disposition of ligand coordination sites. To explore this, the fluorenone scaffold was used to synthesize two other tetradentate ligands (L2 and L3) that differed in the spatial distributions of their coordination vectors. The self-assembly of these ligands with [Pd(en)(ONO2)2] (M2) resulted in the formation of water-soluble (M2)6(L1/L2/L3)3 trifacial tubes of different geometries with varying internal cavity dimensions. These angular variations further altered the orientation of the fluorenone carbonyl groups within the cavities, thereby modulating their guest binding abilities and highlighting the importance of tailoring supramolecular hosts for specific guest binding
Flexible Crystals, Polymorph Selection and Interface Engineering for Organic Electronics: How New Discoveries and Established Knowledge Can Provide New Stimuli for Research Into Organic Semiconducting Single Crystals
No full textOrganic Semiconducting Single Crystals (OSSCs) have long been considered promising materials for organic electronics, due to their high charge carrier mobilities and structural order. However, progress in this field remains limited due to issues such as mechanical fragility, lack of reproducibility of device performance, and difficulties in controlling crystal orientation during integration. Emerging research in three key areas offers new opportunities to overcome these challenges. First, mechanical flexibility, observed in several organic single crystals, is revealing potential for mechanically robust devices. Second, advances in polymorph control, inspired by pharmaceutical crystallography, are enabling more precise control over crystal phase formation. Third, interface engineering, particularly via self-assembled monolayers (SAMs), is proving effective in directing nucleation, polymorph selection, and improving crystal alignment and device performance. Here, the recent progress in these areas is summarized. The structural basis and functional implications of mechanical flexibility in OSSCs are examined, current crystal growth techniques are surveyed, focusing on solution-based methods, and the role of SAMs in tuning interfaces for improved polymorph selection and material performance is evaluated. Remaining bottlenecks hindering large-scale application of OSSCs are identified, and the reviewed topics are proposed as pathways to revitalize OSSC research and accelerate their application in organic electronics
Guest-Shape-Directed Structural Switching between Two Isomers of a Pd6 Host and Its Structural Adaptability for Selective Photodimerization
No full textThe structure and functions of metal–organic cages are heavily dependent on the nature of the building blocks. Herein, a dimethyl-substituted propane diamine blocked cis-Pd(II) acceptor (A) was designed, which upon self-assembly with the tri-imidazole ligand (L), generated an unusual A6L4 octahedral cage (M1O) instead of the expected isomeric double-square architecture that was obtained from the tetramethyl-substituted ethylene diamine blocked cis-Pd(II) acceptor in water. Interestingly, in the presence of planar guests (Gn), M1O showed a transformation to a transient double-square architecture (M1DS), forming host–guest complexes with two such guests, (Gn)2@M1DS. The transient double-square cage (M1DS) readily converts back to the parent octahedral structure, M1O upon the removal of the guests. On the contrary, tetrahedral guests (G5/G6) stabilized the octahedral isomer of the host (M1O) by acting as suitable templates. Additionally, tetrahedral guests could induce the reverse transformation of M1DS to M1O by driving out planar guests from metastable M1DS. The specific antiparallel orientation and proximity of two anthracene derivatives within M1DS enabled them to be selectively transformed to the trans isomers of their respective dimers under photoirradiation. Upon dimer formation, the nonplanar product was expelled readily from the cavity of M1DS, and the host switched back to its original octahedral form (M1O), which functionally and structurally imitates enzymatic activity. Thus, a multifunctional supramolecular host was obtained that showed unique guest-shape-driven reversible structural switching and acted as an adaptive host for selective photodimerization
Stimuli‐Mediated Structural Interchange Between Pd6 and Pd12 Architectures: Selective Recognition of E‐Stilbene by the Pd6 Architecture and its Photoprotection
Full text linkThe dynamic behaviour of metal-ligand bonding cultivates stimuli-mediated structural transformations in self-assembled molecular architectures. The propensity of synthetically designed self-assembled systems to interchange between higher-order architectures is increased multi-fold when the building blocks have higher conformational degrees of freedom. Herein, we report a new ligand, (2,7-bis(di(pyridin-4-yl)amino)-9H-fluoren-9-one) (L), which, upon self-assembly with a cis-[(ethylene-1,2-diamine)Pd(NO3)2] acceptor (M), resulted in the formation of a M6L3 trifacial barrel (C1) in water. Interestingly, during crystallization, a rare M12L6 triangular orthobicupola architecture (C2) was generated along with C1. C2 could also be generated in solution via the application of several stimuli. C1 in aqueous media could stabilize one trans-stilbene (tS) or cis-stilbene (cS) molecule in its cavity, with a selectivity for the former from their mixture. Moreover, C1 acted as an effective host to prevent the otherwise facile photoisomerization of tS to cS inside its hydrophobic cavity under UV irradiation. Conversely, the visible-light-induced reverse isomerization of encapsulated cS to encapsulated tS could be achieved readily due to the better stabilization of tS within the cavity of C1 and its transparency to visible light. A multi-functional system was therefore designed, which at the same time is stimuli-responsive, shows isomer selectivity, and photo-protects trans-stilbene
Self-Assembly of a Water-Soluble Pd16 Square Bicupola Architecture and Its Use in Aerobic Oxidation in Aqueous Medium
Full text linkDesigning supramolecular architectures with uncommon geometries has always been a key goal in the field of metal-ligand coordination-driven self-assembly. It acquires added significance if functional building units are employed in constructing such architectures for fruitful applications. In this report, we address both these aspects by developing a water-soluble Pd16L8 coordination cage 1 with an unusual square orthobicupola geometry, which was used for selective aerobic oxidation of aryl sulfides. Self-assembly of a benzothiadiazole-based tetra-pyridyl donor L with a ditopic cis-[(tmeda)Pd(NO3)2] acceptor [tmeda = N,N,N',N'-tetramethylethane-1,2-diamine] produced 1, and the geometry was determined by single-crystal X-ray diffraction study. Unlike the typically observed tri- or tetrafacial barrel, the present Pd16L8 coordination assembly features a distinctive structural topology and is a unique example of a water-soluble molecular architecture with a square orthobicupola geometry. Efficient and selective aerobic oxidation of sulfides to sulfoxides is an important challenge as conventional oxidation generally leads to the formation of sulfoxide along with toxic sulfone. Cage 1, designed with a ligand containing a benzothiadiazole moiety, demonstrates an ability to photogenerate reactive oxygen species (ROS) in water, thus enabling it to serve as a potential photocatalyst. The cage showed excellent catalytic efficiency for highly selective conversion of alkyl and aryl sulfides to their corresponding sulfoxides, therefore without the formation of toxic sulfones and other byproducts, under visible light in aqueous medium
Postassembly Modification of a Pd6 Host and C70 Encapsulation to Enhance Its ROS-Mediated Terpene Oxidation Ability under Visible Light
No full textThe properties of supramolecules can be modulated by post-assembly modification (PAM) of their building blocks or via guest encapsulation. This work demonstrates a largely uncharted approach to property modulation that integrates both PAM and guest encapsulation in a single system to boost photocatalytic activity. Self-assembly of a “phenothiazine”-functionalized ligand (L) with a cis-blocked Pd(II) acceptor (A) generated an A6L3 trifacial tube (T). Postassembly, T could be modified via irradiation with violet light, leading to the sulfoxidation of the “phenothiazine” moieties in T and thereby generating an oxidized tube (TO). Both TO and T could stabilize a C70 molecule within their cavities, forming C70@TO and C70@T, respectively. Although T showed relatively poor photocatalytic performance mediated by reactive oxygen species (ROS) with respect to oxidation of terpenes (S1–S4) under visible light, the modified TO was much better in that regard. Expectedly, C70@T showed better photocatalytic performance than T due to the presence of photosensitizing C70. While PAM or guest encapsulation alone led to reasonable improvements in photocatalytic ability, their combination within C70@TO led to a significant improvement. Catalytic amounts of C70@TO could instantly oxidize terpenes. Thus, we report here a new host that integrates the effects of both PAM and photosensitizer encapsulation for synergistically boosting its photocatalytic activity
Analysis of the crystal structure of a parallel three‐stranded coiled coil
Full text linkHere, we present the crystal structure of the synthetic peptide KE1, which contains four K-coil heptads separated in the middle by the QFLMLMF heptad. The structure determination reveals the presence of a canonical parallel three stranded coiled coil. The geometric characteristics of this structure are compared with other coiled coils with the same topology. Furthermore, for this topology, the analysis of the propensity of the single amino acid to occupy a specific position in the heptad sequence is reported. A number of viral proteins use specialized coiled coil tail needles to inject their genetic material into the host cells. The simplicity and regularity of the coiled coil arrangement made it an attractive system for de novo design of key molecules in drug delivery systems, vaccines, and therapeutics
Pseudo-Polymorphism in 2-Pyridylmethoxy Cone Derivatives of <i>p-tert</i>-butylcalix[4]arene and <i>p-tert</i>-butylhomooxacalix[n]arenes
Full text linkThis paper investigates pseudo-polymorphism in 2-pyridylmethoxy derivatives of p-tert-butylcalix[4]arene (PyC4), p-tert-butyldihomooxa-calix[4]arenes (PyHOC4), and p-tert-butylhexahomotrioxacalix[3]arenes (PyHO3C3), presenting 11 crystal structures with 15 crystallographically independent molecules. The macrocycle of PyC4 is smaller and less flexible with respect to those of PyHOC4 and PyHO3C3, and in solution, the cone conformation of these three molecules exhibits different point symmetries: C4, Cs, and C3, respectively. A correlation is observed between the macrocycle’s structural rigidity and the number of pseudo-polymorphs formed. The more rigid PyC4 displays a higher number (six) of pseudo-polymorphs compared to PyHOC4 and PyHO3C3, which exhibit a smaller number of crystalline forms (three and two, respectively). The X-ray structures obtained show that the conformation of the macrorings is primarily influenced by the presence of an acetonitrile guest molecule within the cavity, with limited impact from crystal packing and intermolecular co-crystallized solvent molecules. Notably, both calix[4]arene derivatives produce a host–guest complex with acetonitrile, while the most flexible and less aromatic PyHO3C3 does not give crystals with acetonitrile as the guest. Intertwined 1D and 2D solvent channel networks were observed in the PyHOC4-hexane and in the PyHO3C3-H2O-MeOH crystal structures, respectively, while the other pseudopolymorphs of PyHOC4 and PyHO3C3 and all PyC4 crystal forms exhibit closely packed crystal structures without open channels
Vitamin B12 in Foods, Food Supplements, and Medicines—A Review of Its Role and Properties with a Focus on Its Stability
Full text linkVitamin B12, also known as the anti-pernicious anemia factor, is an essential micronutrient totally dependent on dietary sources that is commonly integrated with food supplements. Four vitamin B12 forms—cyanocobalamin, hydroxocobalamin, 5′-deoxyadenosylcobalamin, and methylcobalamin—are currently used for supplementation and, here, we provide an overview of their biochemical role, bioavailability, and efficacy in different dosage forms. Since the effective quantity of vitamin B12 depends on the stability of the different forms, we further provide a review of their main reactivity and stability under exposure to various environmental factors (e.g., temperature, pH, light) and the presence of some typical interacting compounds (oxidants, reductants, and other water-soluble vitamins). Further, we explore how the manufacturing process and storage affect B12 stability in foods, food supplements, and medicines and provide a summary of the data published to date on the content-related quality of vitamin B12 products on the market. We also provide an overview of the approaches toward their stabilization, including minimization of the destabilizing factors, addition of proper stabilizers, or application of some (innovative) technological processes that could be implemented and contribute to the production of high-quality vitamin B12 products
Quadrupling the PLQY of Tetraphenylethylene by Covalently Linking it with Isosteric Tetraarylaminoborane: A Potential Candidate for Multicolor Live Cell Imaging
No full textApplications of organic luminophores depend on their photoluminescence quantum yield (PLQY). Several strategies have been developed to improve the PLQY of organic solids, and one such method is aggregation-induced emission (AIE). Herein, we disclose a comprehensive study of two molecularly engineered covalently linked isosteric AIEgens, BNTPE-1 and BNTPE-2. The independent isosteres tetraarylaminoborane (BN) and tetraphenylethylene (TPE) showed poor PLQY; however, the covalently linked BNTPE-1 and BNTPE-2 systems showed 4 times higher PLQY than the independent isosteres (∼78 and ∼92% for solids and aggregates, respectively). Detailed optical, structural, and computational studies revealed that BN and TPE moieties adopt more coplanarity and have stronger donor (-NPh2)-acceptor (BMes2) interactions in the covalently linked systems than do simple BN and TPE units. Despite having sterically demanding BMes2 units, these compounds are nonemissive in the solution state due to the presence of flexible TPE units. However, they are strongly emissive in condensed states, such as aggregates in solution and the solid state. The excited state structure analysis revealed that the TPE unit undergoes severe conformational distortion after photoexcitation, which activates nonradiative decay channels and consequently quenches the luminescence in the molecularly dispersed state. The bioimaging potential of BNTPE-1 and BNTPE-2 was also explored. These compounds showed high biocompatibility and stained the HeLa cells brighter than BN and TPE molecules
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