ABSTRACT
Now that the chemistry of 1 : 1 host:guest complexes is well-established, it is surprising to note that higher stoichiometry (oligomeric) complexes, especially those with excess host, remain largely unexplored. Yet, proteins tend to oligomerize, affording new functions for cell machinery. Here, we show that cucurbit[n]uril (CB[n]) macrocycles combined with symmetric, linear di-viologens form unusual 3 : 2 host:guest complexes exhibiting remarkable dynamic properties, host self-sorting, and external ring-translocation. These results highlight the structural tunability of cucurbit[8]uril (CB[8]) based 3 : 2 host:guest complexes in water and their responsiveness toward several stimuli (chemicals, pH, redox).
ABSTRACT
We herein report the synthesis and magnetic properties of a Ni(II)-porphyrin tethered to an imidazole ligand through a flexible electron-responsive mechanical hinge. The latter is capable of undergoing a large amplitude and fully reversible folding motion under the effect of electrical stimulation. This redox-triggered movement is exploited to force the axial coordination of the appended imidazole ligand onto the square-planar Ni(II) center, resulting in a change in its spin state from low spin (S = 0) to high spin (S = 1) proceeding with an 80% switching efficiency. The driving force of this reversible folding motion is the π-dimerization between two electrogenerated viologen cation radicals. The folding motion and the associated spin state switching are demonstrated on the grounds of NMR, (spectro)electrochemical, and magnetic data supported by quantum calculations.
Subject(s)
Nickel , Porphyrins , Electric Stimulation , Imidazoles , Ligands , Nickel/chemistry , ViologensABSTRACT
Ditopic bis-(triazole/pyridine)viologens are bidentate ligands that self-assemble into coordination polymers. In such photo-responsive materials, light irradiation initiates photo-induced electron transfer to generate π-radicals that can self-associate to form π-dimers. This leads to a cascade of events: processes at the supramolecular scale associated with mechanical and structural transition at the macroscopic scale. By tuning the irradiation power and duration, we evidence the formation of aggregates and gels. Using microscopy, we show that the aggregates are dense, polydisperse, micron-sized, spindle-shaped particles which grow in time. Using microscopy and time-resolved micro-rheology, we follow the gelation kinetics which leads to a gel characterized by a correlation length of a few microns and a weak elastic modulus. The analysis of the aggregates and the gel states vouch for an arrested phase separation process, a new scenario to supramolecular systems.
ABSTRACT
A viologen-phenylene-imidazole (VPI) conjugate, previously shown to be singly complexed by CB[7] and doubly bound by CB[8], is herein shown to form antiparallel triple stacks in water with cucurbit[10]uril (CB[10]), pairwise complexing the guest trimer. The quinary host:guest 2:3 complex showed features assignable to charge-transfer interactions. Under reductive conditions, CB[10] could solubilize a VPI radical, even though CB[10] and reduced VPI are almost insoluble, thereby illustrating a possible new application for CB[10].
ABSTRACT
A metal-induced self-assembly strategy is used to promote the π-dimerization of viologen-based radicals at room temperature and in standard concentration ranges. Discrete box-shaped 2:2 (M:L) macrocycles or coordination polymers are formed in solution by self-assembly of a viologen-based ditopic ligand with cis-[Pd(en)(NO3)2], trans-[Pd(CH3CN)2(Cl)2], or [Pd(CH3CN)4(BF4)2]. Changing the redox state of the bipyridium units involved in the tectons, from their dicationic state to their radical cation state, results in a reversible "inflation/deflation" of the discrete 2:2 (M:L) macrocyclic assemblies associated to a large modification in the size of their inner cavity. Viologen-centered electron transfer is also used to trigger a dissociation of the coordination polymers formed with tetrakis(acetonitrile)Pd(II), the driving force of the disassembling process being the formation of discrete box-shaped 2:2 (M:L) assemblies stabilized by π-dimerization of both viologen cation radicals.
ABSTRACT
The development of heterogeneous catalysts capable of selectively converting lignin model compounds into products of added value offers an exciting avenue to explore in the production of renewable chemical feedstocks. The use of metal-organic frameworks (MOFs) in such chemical transformations relies largely on the presence of accessible open metal sites found within highly porous networks that simultaneously allow for fast transport and strong interactions with desired substrates. Here, we present the first systematic study on the modulation of catalytic performance of a cationic framework, [Cu2(L)(H2O)2](NO3)2·5.5H2O (L = 1,1'-bis(3,5-dicarboxylatophenyl)-4,4'-bipyridinium), achieved through the exchange of anionic guests. Remarkably, the catalytic activity proves to be highly anion-dependent, with a nearly 10-fold increase toward the aerobic C-C bond cleavage of a lignin model compound when different anionic species are incorporated within the MOF. Moreover, we demonstrate that the cationic nature of the MOF, imparted by the incorporation of viologen moieties within the linker, tunes the electrophilicity of the active copper(II) sites, resulting in stronger interactions with the substrate. As such, the copper-based framework exhibits enhanced catalytic performance when compared to its neutral counterpart, emphasizing the appeal of charged frameworks for use as green heterogeneous catalysts.
ABSTRACT
A halogen-bond templated 1:1 macrocyclization in solution is reported. Tetra(iodoperfluorophenyl) ethers were used as halogen-bonded exotemplates in a substoichiometric amount (5â mol %). Pyridine-containing macrocyclic architectures were formed by ruthenium-catalyzed tandem metathesis/transfer hydrogenation sequence using sodium borohydride and methanol as non-dihydrogen hydrogen source. The halogen-bonded stabilization energies were analyzed relying on density functional theory.
ABSTRACT
A dynamic supramolecular approach is developed to promote the π-dimerization of viologen radicals at room temperature and in standard concentration ranges. The approach involves cis- or trans-protected palladium centers serving as inorganic hinges linking two functionalized viologens endowed with metal-ion coordinating properties. Based on detailed spectroscopic, electrochemical and computational data, we show that the one-electron electrochemical reduction of the viologen units in different dynamic metal/ligand mixtures leads to the formation of the same intramolecular π-dimer, regardless of the initial environment around the metallic precursor and of the relative ratio between metal and ligand initially introduced in solution. The large-scale electron-triggered reorganization of the building blocks introduced in solution thus involves drastic changes in the stoichiometry and stereochemistry of the palladium/viologen complexes proceeding in some cases through a palladium centered transâcis isomerization of the coordinated ligands.
ABSTRACT
We have developed a strategy enabling control over the organization of ditopic molecular tectons within a palladium-based self-assembled system. The key electron-responsive sub-unit is a viologen-based mechanical hinge that can toggle under electric stimulation between a folded and a stretched position, the driving force of the folding motion being the π-dimerisation of the electrogenerated viologen cation radicals. The title ditopic tecton features two planar, N2-type, triazole/pyridine-based bidentate binding units, providing the tecton with the ability to chelate two palladium ions both in its folded and in its elongated conformations. Association of this ditopic redox-responsive tecton with palladium to form 1D self-assembled architectures undergoing large scale reorganizations in solution under electric stimulation, has been established on the ground of spectroscopic, electrochemical, spectro-electrochemical and rheological data. Our result reveal that addition of metal leads to a significant stabilization of the π-dimer species in solution and that the redox-triggered reorganisation of the tectons comes along in suitable conditions with a macroscopic sol/gel-type phase transition.
ABSTRACT
A series of alternating 3,4-ethylenedioxythiophene-alkynylpyridine oligomers (DA)n with increased solubility are synthesized and their photophysical properties and nonlinear optical properties are investigated. Their quadratic polarizabilities are determined from hyper-Rayleigh scattering experiments to obtain information on their conformations in solution. These chromophores, based on the alternation of electron-rich (D) and electron-deficient (A) moieties, exhibit optical properties that arise from the combination of dipolar and helicoidal features in the (DA)n homologue series where n=1-4. The transition from dipolar conjugated planar structures (n=1, 2) to helicoidal structures (n=3, 4) is clearly evidenced by results from symmetry-sensitive second-order nonlinear optical experiments. This suggests an approach towards highly efficient chiral chromophores for second-order nonlinear optics. Interestingly, this structural evolution also has significant impact on the photophysical properties: both absorption and fluorescence emission show bathochromic and hyperchromic shifts with increasing number of repeating units in the dipolar planar derivatives (n=1-2) but show saturation effects in the helicoidal structures (n=2-4). In addition, the helicoidal structures show sizeable two-photon absorption at 700-750â nm (40-100â GM) for compounds lacking either electron-donating or electron-withdrawing substituents.
ABSTRACT
The synthesis of N-arylated pyrroles and indoles is documented, as well as their functionalization by deprotonative metallation using the base in situ prepared from LiTMP and ZnCl2·TMEDA (1/3 equiv). With N-phenylpyrrole and -indole, the reactions were carried out in hexane containing TMEDA which regioselectively afforded the 2-iodo derivatives after subsequent iodolysis. With pyrroles and indoles bearing N-substituents such as 2-thienyl, 3-pyridyl, 4-methoxyphenyl and 4-bromophenyl, the reactions all took place on the substituent, at the position either adjacent to the heteroatom (S, N) or ortho to the heteroatom-containing substituent (OMe, Br). The CH acidities of the substrates were determined in THF solution using the DFT B3LYP method in order to rationalize the experimental results.
ABSTRACT
1-Aryl- and 2-aryl-1,2,3-triazoles were synthesized by N-arylation of the corresponding azoles using aryl iodides. The deprotometalations of 1-phenyl-1,2,3-triazole and -1,2,4-triazole were performed using a 2,2,6,6-tetramethylpiperidino-based mixed lithium-zinc combination and occurred at the most acidic site, affording by iodolysis the 5-substituted derivatives. Dideprotonation was noted from 1-(2-thienyl)-1,2,4-triazole by increasing the amount of base. From 2-phenyl-1,2,3-triazoles, and in particular from 2-(4-trifluoromethoxy)phenyl-1,2,3-triazole, reactions at the 4 position of the triazolyl, but also ortho to the triazolyl on the phenyl group, were observed. The results were analyzed with the help of the CH acidities of the substrates, determined in THF solution using the DFT B3LYP method. 4-Iodo-2-phenyl-1,2,3-triazole and 4-iodo-2-(2-iodophenyl)-1,2,3-triazole were next involved in Suzuki coupling reactions to furnish the corresponding 4-arylated and 4,2'-diarylated derivatives. When evaluated for biological activities, the latter (which are resveratrol analogues) showed moderate antibacterial activity and promising antiproliferative effect against MDA-MB-231 cell line.
Subject(s)
Antineoplastic Agents/chemistry , Stilbenes/chemistry , Triazoles/chemistry , Anti-Bacterial Agents/chemical synthesis , Anti-Bacterial Agents/chemistry , Anti-Bacterial Agents/pharmacology , Antineoplastic Agents/chemical synthesis , Antineoplastic Agents/pharmacology , Cell Line, Tumor , Cell Proliferation/drug effects , Crystallography, X-Ray , Gram-Negative Bacteria/drug effects , Gram-Positive Bacteria/drug effects , Humans , Microbial Sensitivity Tests , Molecular Conformation , Resveratrol , Stilbenes/chemical synthesis , Stilbenes/pharmacologyABSTRACT
Substituted azafluorenones were synthesized from different dihalogeno diaryl ketones under palladium catalysis by combining either Suzuki or Heck coupling with direct cyclizing arylation. Conditions were identified to allow both auto-tandem processes to proceed successfully from 3-(bromobenzoyl)- or 3-benzoyl-4-bromo-2-chloropyridines, as well as 4-benzoyl-2,3- and 4-benzoyl-2,5-dichloropyridines.
Subject(s)
Aza Compounds/chemical synthesis , Fluorenes/chemical synthesis , Ketones/chemistry , Palladium/chemistry , Aza Compounds/chemistry , Catalysis , Fluorenes/chemistry , Molecular StructureABSTRACT
Recent advances in the selective deprotometallation of aromatic reagents using alkali metal cuprates are reported. The ability of these synergic bases to effect deprotonation under the influence of a directing group is explored in the context of achieving new and more efficient organic transformations whilst encouraging greater ancillary group tolerance by the base. Developments in our understanding of the structural chemistry of alkali metal cuprates are reported, with both Gilman cuprates of the type R2CuLi and Lipshutz and related cuprates of the type R2Cu(X)Li2 (X = inorganic anion) elucidated and rationalised in terms of ligand sterics. The generation of new types of cuprate motif are introduced through the development of adducts between different classes of cuprate. The use of DFT methods to interrogate the mechanistic pathways towards deprotonative metallation is described. Theoretical modelling of in situ rearrangements undergone by the cuprate base are discussed, with a view to understanding the relationship between R2CuLi and R2Cu(X)Li2, their interconversion and the implications of this for cuprate reactivity. The advent of a new class of adduct between different cuprate types is developed and interpreted in terms of the options for expelling LiX from R2Cu(X)Li2. Applications in the field of medicinal chemistry and (hetero)arene derivatization are explored.
Subject(s)
Copper/chemistry , Hydrocarbons, Aromatic/chemistry , Metals, Alkali/chemistry , Organometallic Compounds/chemistry , Models, MolecularABSTRACT
Benzothiophene, benzofuran, benzothiazole and benzoxazole were deprotometalated using the lithium-zinc combination prepared from ZnCl2·TMEDA (TMEDA=N,N,N',N'-tetramethylethylenediamine, 1equiv) and lithium 2,2,6,6-tetramethylpiperidide (LiTMP, 3equiv). Subsequent interception of the 2-metalated derivatives using iodine as electrophile led to the iodides in 81%, 82%, 67% and 42% yields, respectively. These yields are higher (10% more) than those obtained using ZnCl2·TMEDA (0.5equiv) and LiTMP (1.5equiv), except in the case of benzoxazole (10% less). The crude iodides were involved in the N-arylation of pyrrole, indole, carbazole, pyrazole, indazole, imidazole and benzimidazole in the presence of Cu (0.2equiv) and Cs2CO3 (2equiv), and using acetonitrile as solvent (no other ligand) to provide after 24h reflux the expected N-arylated azoles in yields ranging from 33% to 81%. Using benzotriazole also led to N-arylation products, but in lower 34%, 39%, 36% and 6% yields, respectively. A further study with this azole evidenced the impact of 2,2,6,6-tetramethylpiperidine on the N-arylation yields. Most of the C,N'-linked bis-heterocycles thus synthesized (in particular those containing benzimidazole) induced a high growth inhibition of A2058 melanoma cells after a 72h treatment at 10(-5)M.
Subject(s)
Antineoplastic Agents/pharmacology , Heterocyclic Compounds/pharmacology , Iodides/pharmacology , Melanoma/drug therapy , Triazoles/pharmacology , Antineoplastic Agents/chemical synthesis , Antineoplastic Agents/chemistry , Cell Line, Tumor , Cell Proliferation/drug effects , Dose-Response Relationship, Drug , Drug Screening Assays, Antitumor , Heterocyclic Compounds/chemical synthesis , Heterocyclic Compounds/chemistry , Humans , Iodides/chemistry , Melanoma/pathology , Models, Molecular , Molecular Structure , Structure-Activity Relationship , Triazoles/chemistryABSTRACT
1-Aryl-1H-benzotriazoles and -1H-indazoles were synthesized, and their deproto-metallation using the base prepared by mixing LiTMP with ZnCl2·TMEDA (1/3 equiv.) was studied. In the indazole series, reactions occurring at the 3 position were followed by ring opening, and functionalization of the substrate was only found possible (on the sulfur ring) using 2-thienyl as aryl group. In the benzotriazole series, either mono- or bis-deprotonation (depending on the amount of base employed) was achieved with phenyl, 4-methoxyphenyl and 2-thienyl as aryl group, and bis-deprotonation in the case of 4-chlorophenyl and 4-trifluoromethylphenyl. The experimental results were analyzed with the help of the CH acidities of the substrates, determined in THF solution using the DFT B3LYP method.
Subject(s)
Indazoles/chemical synthesis , Lithium/chemistry , Organometallic Compounds/chemistry , Triazoles/chemical synthesis , Zinc/chemistry , Indazoles/chemistry , Models, Molecular , Organometallic Compounds/chemical synthesis , Quantum Theory , Triazoles/chemistryABSTRACT
The construction of pyridine-containing macrocyclic architectures using a nonmetallic template is described. 4,6-Dichlororesorcinol was used as an exotemplate to self-organize two aza-heterocyclic units by OH···N hydrogen bonds. Subsequent sequential double olefin metathesis/hydrogenation reactions employing a single ruthenium-alkylidene precatalyst open access to macrocyclic molecules.
Subject(s)
Alkenes/chemistry , Macrocyclic Compounds/chemistry , Pyridines/chemistry , Resorcinols/chemistry , Ruthenium/chemistry , Catalysis , Cyclization , Hydrogen Bonding , Hydrogenation , Molecular StructureABSTRACT
With the aim of synthesizing biaryl compounds, several aromatic iodides were prepared by the deprotonative metalation of methoxybenzenes, 3-substituted naphthalenes, isoquinoline, and methoxypyridines by using a mixed lithium/zinc-TMP (TMP=2,2,6,6-tetramethylpiperidino) base and subsequent iodolysis. The halides thus obtained, as well as commercial compounds, were cross-coupled under palladium catalysis (e.g., Suzuki coupling with 2,4-dimethoxy-5-pyrimidylboronic acid) to afford various representative biaryl compounds. Deprotometalation of the latter compounds was performed by using the lithium/zinc-TMP base and evaluated by subsequent iodolysis. The outcome of these reactions has been discussed in light of the CH acidities of these substrates, as determined in THF solution by using the DFT B3LYP method. Except for in the presence of decidedly lower pKa values, the regioselectivities of the deprotometalation reactions tend to be governed by nearby coordinating atoms rather than by site acidities. In particular, azine and diazine nitrogen atoms have been shown to be efficient in inducing the reactions with the lithium/zinc-TMP base at adjacent sites (e.g., by using 1-(2-methoxyphenyl)isoquinoline, 4-(2,5-dimethoxyphenyl)-3-methoxypyridine, or 5-(2,5-dimethoxyphenyl)-2,4-dimethoxypyrimidine as the substrate), a behavior that has already been observed upon treatment with lithium amides under kinetic conditions. Finally, the iodinated biaryl derivatives were involved in palladium-catalyzed reactions.
Subject(s)
Heterocyclic Compounds/chemical synthesis , Hydrocarbons, Iodinated/chemistry , Lithium/chemistry , Palladium/chemistry , Piperidines/chemical synthesis , Zinc/chemistry , Amides/chemistry , Catalysis , Combinatorial Chemistry Techniques , Heterocyclic Compounds/chemistry , Kinetics , Models, Chemical , Molecular Structure , Piperidines/chemistryABSTRACT
2-Aryl-1,2,3-triazoles were synthesized by cyclization of the corresponding glyoxal arylosazones, generated from commercial arylhydrazines. The deproto-metallation of 2-phenyl-1,2,3-triazole was attempted using different 2,2,6,6-tetramethylpiperidino-based mixed lithium-metal (Zn, Cd, Cu, Co, Fe) combinations, giving results in the case of Zn, Cd, and Cu. The lithium-zinc combination was next selected to apply the deprotonation-iodination sequence to all the 2-aryl-1,2,3-triazoles synthesized. The results were analyzed with the help of the CH acidities of the substrates, determined in THF solution using the DFT B3LYP method.