1,721,372 research outputs found
Self-assembly of a redox active water soluble Pd6L8‘molecular dice’
No full textA water soluble ‘molecular dice’ was synthesised via coordination driven self-assembly of a Pd(II) ion with a flexible cationic tritopic donor and was fully characterised using NMR, ESI-MS and single crystal X-ray diffraction analysis. The donor-inherited redox active nature of the ‘molecular dice’ was studied using cyclic voltammetry
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
A Discrete Self-Assembled Pd-12 Triangular Orthobicupola Cage and its Use for Intramolecular Cycloaddition
No full textWater-soluble Pd12L6 coordination cage TC-1 was synthesized by coordination-driven self-assembly of symmetrical tetrapyridyl donor L with 90 degrees ditopic acceptor cis-Pd(NO3)(2)(tmeda)] tmeda=N,N,N,N-tetramethylethane-1,2-diamine]. The Pd12L6 coordination assembly is an uncommon example of a coordination cage having triangular orthobicupola-like geometry. It was characterized by multinuclear NMR spectroscopy, ESI-MS, and single-crystal X-ray diffraction. Self-assembly of a tetratopic donor with a cis-blocked 90 degrees ditopic acceptor generally yields tri-/tetra-/hexagonal barrels or closed cubic cages. However, in the present case the donor and acceptor are arranged in an unusual fashion to generate an orthobicupola geometry in which two triangular cupola share a common irregular hexagonal face. The cage was used to perform intramolecular cycloaddition reactions of O-propargylated benzylidinebarbituric acid derivatives in nitromethane. Several penta-/tetracyclouracil derivatives were synthesized through cage-catalyzed 4+2] cycloaddition reactions in a concerted manner with good to high conversion under mild reaction conditions, whereas in the absence of cage TC-1 similar reactions led to lower conversion to the cyclized products in organic solvent. This approach is of particular importance compared to the literature reports on the synthesis of similar compounds under high-temperature reflux conditions with high catalyst loading
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
Coordination-Driven Self-Assembly of Discrete Molecular Nanotubular Architectures
No full textTwo new M8L4 tetrafacial nanotubes (T1 and T3) of different lengths have been synthesized in water using ligands L1 and L2, respectively, with acceptor cis-[(dch)Pt(NO3)2] (M) using coordination-driven self-assembly [where dch is 1,2-diaminocyclohexane, L1 is 1,4-di(pyrimidin-5-yl)benzene, and L2 is 4,4′- di(pyrimidin-5-yl)-1,1′-biphenyl]. In addition to complex T1, a tetrahedral cage of composition [M12(L1)6] (T2) was also formed in the self-assembly reaction of ligand L1 with cis-[(dch)Pt(NO3)2]. The precise composition of the products (T1 and T2) in solution was confirmed by 1H NMR and ESI–MS. Pure tube T1 was separated out by a crystallization technique and fully characterized by 1H NMR and X-ray diffraction. Temperature- and concentration-dependent NMR studies indicated no equilibrium between T1 and T2 in the solution phase, and the proportion of T1 and T2 in the mixture depends on the temperature of the reaction. In contrast to ligand L1, the self-assembly of the longer ligand, L2, with cis-[(dch)Pt(NO3)2] gave only tetrafacial tube [M8(L2)4] (T3) without any tetrahedral cage
Host–Guest Interactions Induced Enhancement in Oxidase-Like Activity of a Benzothiadiazole Dye Inside an Aqueous Pd8L4 Barrel
No full textThe effect of host-guest interactions on the chemistry of encapsulated molecules is a fascinating field of research that has gained momentum in recent years. Much of the work in this field has been focused on the effect of such interactions on catalysis and photoluminescence of encapsulated dyes. However, the effect of such interactions on related photoinduced processes, such as photoregulated oxidase-mimicking activity, has not been explored much. Herein, we report a unique example of enhancement of oxidase-like activity of a benzothiadiazole dye (G1) in water through encapsulation within a M8L4 molecular barrel (1). Favorable host-guest interactions helped the encapsulated guest G1 to have better photoinduced electron transfer to molecular oxygen leading to increased production of superoxide radical anions and oxidase-like activity. Furthermore, encapsulation inside 1 also caused a change in the redox potentials of the guest (G1) which after photoinduced electron transfer produced a better oxidizing agent than free G1. These phenomena combined to enhance the oxidase-like activity of dye G1 upon encapsulation inside cage 1. The present report demonstrates a unique effect of host-guest chemistry on photoregulated processes
Cavity-Shape-Dependent Divergent Chemical Reaction inside Aqueous Pd6L4 Cages
Full text linkChemical reactions inside the confined pockets of enzyme-mimicking hosts, such as cages and macrocycles, have been an emerging field of interest over the past decade. Although many such reactions are known, the use of such cages toward the divergent synthesis of nonisomeric products has not been well explored. Divergent synthesis is a technique of forming two or more distinct products from the same reagents by changing the catalyst or reaction conditions. Changing the shape of the cage can also change the nature and magnitude of the host-guest interactions. Thus, is it possible for such changes to cause differences in the reaction pathways leading to formation of nonisomeric products? Herein, we report a divergent chemical transformation of anthrone [anthracen-9(10H)-one] inside different water-soluble M6L4 cages. When anthrone was encapsulated inside a newly synthesized M6L4 octahedral cage 1, it dimerized to form dianthrone [9,9'-bianthracen-10,10'(9H,9'H)-dione]. In contrast, when the same chemical reaction was performed inside a M6L4 double-square shaped cage 2, it was oxidized to form anthraquinone [anthracene-9,10-dione]. Similar results were obtained with a different set of isomeric aqueous Pd6 cages 3a (octahedral cage) and 3b (double-square cage), indicating the dependence of the shape of cavity on the divergent synthesis. The present report demonstrates a unique example of different outcomes/results of a reaction depending on the shape of the molecular container, which was driven by the host-guest interactions and the preorganization of the substrates
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