3]rotaxane-porphyrin conjugate as a novel supramolecular host for fullerenes

A new supramolecular host with good affinity toward fullerenes has been developed. This host having a tweezer-like shape is built on a [3]rotaxane scaffold and contains two free-base porphyrin moieties as recognition units for fullerenes. The ability of this tweezer to bind fullerenes strongly depends on the solvent system used and the size of fullerene.     

Nanosized polymetallic resorcinarene-based host assemblies that strongly bind fullerenes

Polymetallic nanodimensional assemblies have been prepared via metal directed assembly of dithiocarbamate functionalized cavitand structural frameworks with late transition metals (Ni, Pd, Cu, Au, Zn, and Cd). The coordination geometry about the metal centers is shown to dictate the architecture adopted. X-ray crystallographic studies confirm that square planar coordination geometries result in "cagelike" octanuclear complexes, whereas square-based pyramidal metal geometries favor hexanuclear "molecular loop" structures. Both classes of complex are sterically and electronically complementary to the fullerenes (C(60) and C(70)). The strong binding of these guests occurred via favorable interactions with the sulfur atoms of multiple dithiocarbamate moieties of the hosts. In the case of the tetrameric copper(II) complexes, the lability of the copper(II)-dithiocarbamate bond enabled the fullerene guests to be encapsulated in the electron-rich cavity of the host, over time. The examination of the binding of fullerenes has been undertaken using spectroscopic and electrochemical methods, electrospray mass spectrometry, and molecular modeling.     

A guest-induced reversible switching of a self-assembled H-bonded supramolecular framework

A new class of organic crystalline 2,2'-biphenol-based H-bonded material displaying 1D-channels encapsulating solvent molecules is described. A reversible guest-induced crystal-to-crystal conversion between the solvated H-bonded phase and a compact H-bonded non-solvated phase was observed. The energy competition between intramolecular H-bonds formation and solvation of organic pores has been characterized using PACHA calculations.     

Metalloporphyrin hosts for supramolecular chemistry of fullerenes

This paper is a tutorial review of the host-guest chemistry of fullerenes and metalloporphyrin. Among various host molecules for fullerenes, cyclic hosts composed of metalloporphyrin moieties possess one of the highest affinities toward fullerenes, which can be widely tuned simply by changing the central metal ions of the porphyrin moieties. Inclusion of fullerenes occurs not only by van der Waals interactions but also, in some cases, via pi-electronic charge-transfer from the host metalloporphyrin moieties to the guest fullerenes. Fullerenes such as C(120), upon inclusion with cyclic metalloporphyrin dimers, show an oscillatory motion within the host cavity, whose frequency reflects the solvation/desolvation dynamics of the fullerenes. A molecularly engineered metalloporphyrin host with a self-assembling capability allows a guest-directed formation of a supramolecular peapod, where included fullerenes, as peas, are aligned along the self-assembled metalloporphyrin nanotube, as a pod. Furthermore, certain metalloporphyrin hosts are applicable to the selective extraction of low-abundance higher fullerenes from an industrial production source and also allow spectroscopic discrimination of chiral fullerenes.     

Beta-1,3-glucan polysaccharide (schizophyllan) acting as a one-dimensional host for creating supramolecular dye assemblies

We have demonstrated that one-dimensional supramolecular dye assemblies with a uniform diameter can be created by utilizing schizophyllan (SPG) as a one-dimensional host. In the supramolecular nanofibers, the dye molecules are assembled into the different aggregation modes depending on the preparation procedures. The findings establish that SPG is useful for creating the supramolecular nanofibers, where temporal superstructures can be stabilized by the SPG-specific helical higher-order structure. [structure: see text].     

Dendritic supramolecular assemblies for drug delivery

Dendritic supramolecular assemblies were formed in water with Reichardt's dye or the anticancer drug 10-hydroxycamptothecin and the dendritic macromolecule, ([G4]-PGLSA-OH)2-PEG3400.     

Photoluminescence spectra of self-assembling helical supramolecular assemblies: a theoretical study

The reversible assembly of helical supramolecular polymers of chiral molecular building blocks is known to be governed by the interplay between mass action and the competition between weakly and strongly bound states of these building blocks. The highly co-operative transition from free monomers at high temperatures to long helical aggregates at low temperatures can be monitored by photoluminescence spectroscopy that probes the energetically lowest-lying optical excitations in the assemblies. In order to provide the interpretation of obtained spectroscopic data with a firm theoretical basis, we present a comprehensive model that combines a statistical theory of the equilibrium polymerization with a quantum-mechanical theory that not only accounts for the conformational properties of the assemblies but also describes the impact of correlated energetic disorder stemming from deformations within the chromophores and their interaction with solvent molecules. The theoretical predictions are compared to fluorescence spectra of chiral oligo(p-phenylene-vinylene) molecules in the solvent dodecane and we find them to qualitatively describe the red-shift of the main fluorescence peak and its decreasing intensity upon aggregation.     

3-Substituted-2,4-pentanedionates: ligands for photoactive supramolecular assemblies

Synthetic routes for the construction of 3-substituted 2,4-pentadionate ligands are broadly surveyed. They involve sequential alkylation and arylation by numerous methods, including those based on reactions of coordinated ligands, and can provide access to various rationally designed ligands. Applications of such ligands in the synthesis of multichromophoric complexes are illustrated in some detail. Incorporation of 3-substituted 2,4-pentanedione units into mesomorphic and macromolecular structures is considered in relation to structural control of energy and electron transfer processes in photoactive systems. Aspects of the general supramolecular chemistry of complexes of 3-substituted-2,4-pentadionate ligands are briefly discussed to illustrate the utility of such species within the full range of 1,3-dionate chemistry.     

Organostannoxane-supported multiferrocenyl assemblies: synthesis, novel supramolecular structures, and electrochemistry

Organostannoxane-based multiredox assemblies containing ferrocenyl peripheries have been readily synthesized by a simple one-pot synthesis, either by a solution method or by room-temperature solid-state synthesis, in nearly quantitative yields. The number of ferrocenyl units in the multiredox assembly is readily varied by stoichiometric control as well as by the choice of the organotin precursors. Thus, the reaction of the diorganotin oxides, R2SnO (R = Ph, nBu and tBu) with ferrocene carboxylic acid affords tetra-, di-, and mononuclear derivatives [{Ph2Sn[OC(O)Fc]2}2] (1), [{[nBu2SnOC(O)Fc]2O}2] (2), [nBu2Sn{OC(O)Fc}2] (3), [{tBu2Sn(OH)OC(O)Fc}2] (4), and [tBu2Sn{OC(O)Fc}2] (5) (Fc = eta(5)C5H4-Fe-eta(5)C5H5). The reaction of triorganotin oxides, R3SnOSnR3 (R = nBu and Ph) with ferrocene carboxylic acid leads to the formation of the mono-nuclear derivatives [Ph3SnOC(O)Fc] (6) and [{nBu3SnOC(O)Fc}(n)] (7). Molecular structures of the compounds 1-4 and 6 have been determined by single-crystal X-ray analysis. The molecular structure of compound 1 is new among organotin carboxylates. In this compound, ferrocenyl carboxylates are involved in both chelating and bridging coordination modes to the tin atoms to form an eight-membered cyclic structure. In all of these compounds, the acidic protons of the cyclopentadienyl groups are hydrogen bonded to the carboxylate oxygens (C-HO) to form rich supramolecular assemblies. In addition to this, pi-pi, T-shaped, L-shaped, and side-to-face stacking interactions involving ferrocenyl groups also occur. Compound 6 shows an interesting and novel intermolecular CO2-pi stacking interaction. Electrochemical analysis of the compounds 1-4, 6, and 7 shows a single, quasi-reversible oxidation peak corresponding to the simultaneous oxidation of four, two, and one ferrocenyl substituents, respectively. Compound 5 shows two quasi-reversible oxidation peaks. This is attributed to the positional difference among the ferrocenyl substituents on the tin atom. Additionally, while compounds 2 and 4 are electrochemically quite robust and do not decompose even after ten continuous CV cycles, compounds 1, and 3, 5-7 start to show decomposition after five cycles.     

Preparation of supramolecular chromophoric assemblies using a DNA duplex

Organization of supramolecular assemblies of chromophores with precisely-controlled orientation and sequence remains challenging. Nucleic acids with complementary base sequences spontaneously form double-helical structures. Therefore, covalent attachment of chromophores to DNA or RNA can be used to control assembly and orientation of chromophores. In this perspective, we first review our recent work on the assemblies of fluorophores (pyrene and perylene) by using natural base pairs. The interaction between dyes can be strictly controlled by means of cluster and interstrand wedge motifs. We then discuss novel artificial base pairs that can suppress the interaction between fluorophores and nucleobases. We incorporated a cyclohexane moiety into DNA, and showed that these artificial base pairs suppressed the electron-hole transfer between fluorophores and nucleobases and enhanced the quantum yields of fluorophores. These base pairs can potentially be used to accumulate fluorophores inside DNA duplexes without decreasing quantum yields.     

Exohedral functionalization of fullerenes and supramolecular chemistry

We have investigated the exohedral functionalization of [60]fullerene, especially bisaddition; we have revealed the regioselectivity of bisaddition and the properties of obtained bisadducts. The bisaddition without any restriction generally shows low regioselectivity. The electronic and photophysical properties of bisadducts mainly depend on the addition patterns and are almost independent of the nature of addends. We have also attained the regioselective synthesis of bisadducts by controlling the distance and orientation between two reactive species with suitable covalent templates and their application into some functional materials. The synthesis of fullerene‐containing interlocked molecules, such as catenanes and rotaxanes, was accomplished by using a noncovalent interaction, mainly a donor‐acceptor interaction, in addition to the covalent functionalization. The bistable rotaxanes, which can serve as a molecular shuttle or switch, were also successfully prepared. DOI 10.1002/tcr.201000036     

Stimuli-responsive supramolecular assemblies of linear-dendritic copolymers

With the goal of developing a pH-responsive micelle system, linear-dendritic block copolymers comprising poly(ethylene oxide) and either a polylysine or polyester dendron were prepared and hydrophobic groups were attached to the dendrimer periphery by highly acid-sensitive cyclic acetals. These copolymers were designed to form stable micelles in aqueous solution at neutral pH but to disintegrate into unimers at mildly acidic pH following loss of the hydrophobic groups upon acetal hydrolysis. Micelle formation was demonstrated by encapsulation of the fluorescent probe Nile Red, and the micelle sizes were determined by dynamic light scattering. The structure of the dendrimer block, its generation, and the synthetic method for linking the acetal groups to its periphery all had an influence on the critical micelle concentration and the micelle size. The rate of hydrolysis of the acetals at the micelle core was measured for each system at pH 7.4 and pH 5, and it was found that all systems were stable at neutral pH but underwent significant hydrolysis at pH 5 over several hours. The rate of hydrolysis at pH 5 was dependent on the structure of the copolymer, most notably the hydrophobicity of the core-forming block. To demonstrate the potential of these systems for controlled release, the release of Nile Red as a "model payload" was examined. At pH 7.4, the fluorescence of micelle-encapsulated Nile Red was relatively constant, indicating it was retained in the micelle, while at pH 5, the fluorescence decreased, consistent with its release into the aqueous environment. The rate of release was strongly correlated with the rate of acetal hydrolysis and was therefore controlled by the chemical structure of the copolymer. The mechanism of Nile Red release was investigated by monitoring the change in size of the micelles over time at acidic pH. Dynamic light scattering measurement showed a size decrease over time, eventually reaching the size of a unimer, thus providing evidence for the proposed micelle disintegration.     

Accurate length control of supramolecular oligomerization: Vernier assemblies

Linear oligomeric supramolecular assemblies of defined length have been generated using the Vernier principle. Two molecules, containing a different number (n and m) of mutually complementary binding sites, separated by the same distance, interact with each other to form an assembly of length (n x m). The assembly grows in the same way as simple supramolecular polymers, but at a molecular stop signal, when the binding sites come into register, the assembly terminates giving an oligomer of defined length. This strategy has been realized using tin and zinc porphyrin oligomers as the molecular building blocks. In the presence of isonicotinic acid, a zinc porphyrin trimer and a tin porphyrin dimer form a 3:4 triple stranded Vernier assembly six porphyrins long. The triple strand Vernier architecture introduced here adds an additional level of cooperativity, yielding a stability and selectivity that cannot be achieved via a simple Vernier approach. The assembly properties of the system were characterized using fluorescence titrations and size-exclusion chromatography (SEC). Assembly of the Vernier complex is efficient at micromolar concentrations in nonpolar solvents, and under more competitive conditions, a variety of fragmentation assemblies can be detected, allowing determination of the stability constants for this system and detailed speciation profiles to be constructed.     

Transition-metal-doped aluminum hydrides as building blocks for supramolecular assemblies

Density functional theory calculations were carried out to characterize a series of transition-metal-doped aluminum hydrides, forming TMAl(n)H(2n) and TMAl(n)H(2n+1) (TM = Sc, Ti, V; n = 3,4), in either charged or neutral form. A new electron-counting rule for these clusters was formulated as PSEN (paired skeleton electron number) = 4n, which can characterize both closed-shell and open-shell clusters. On the basis of this electron-counting rule, the superatomic clusters such as TiAl(4)H(9) and TiAl(3)H(6) were identified and can be used to assemble supramolecular structures. Electronic structure analysis showed that three-centered TM-H-Al bonds largely contributed to the structural stability. Also, the spin state of a wide range of clusters in their ground state can be predicted by the electron-counting rule.     

Hydrogen-bonded assemblies of a new polyoxometalate-based 3-D supramolecular architecture

A new hydrogen-bonded 3-D supramolecular architecture [Ni(2,2′-bpy)₃]_1.5[AsW^VI ₁₀W^V ₂O₄₀Ni(2,2′-bpy)₂(H₂O)]·0.5H₂O (2,2′-bpy?=?2,2′-bipyridine) (1) has been hydrothermally synthesized and characterized by single-crystal X-ray diffraction analysis, PXRD, elemental analysis, XPS, and IR spectrum. Compound 1 exhibits photocatalytic activity for methylene blue degradation under visible-light irradiation and shows good stability toward visible-light photocatalysis. Luminescence of 1 is also reported.     

Two-photon degradable supramolecular assemblies of linear-dendritic copolymers

Micelles of dendritic-linear copolymers have been developed to release a payload after infrared stimulus.     

Naphthyridine-based helical foldamers and macrocycles: synthesis, cation binding, and supramolecular assemblies

Unraveling the factors that control the conformation of molecular chains is of great interest both for understanding the shape of biological molecular strands and for designing artificial ones that adopt desired forms. Thus, a variety of artificial folding codons have been identified that enforce the formation, among others, of helices, strands, and loops, the major emphasis being on the shape of the foldamer. We report herein the synthesis and study of a family of foldamers and macrocycles based on the 1,8-naphthyridine and pyrimidine units, whose internal cavity is large enough to accommodate ionic substrates, and focus on the impact of guest binding within a cylindrical environment. Interestingly, the binding event within these large oligomers is translated to the outside of the receptors and affects the interaction of the overall complexes with the outside world. For instance, alkali cations bind to the one-turn helices and macrocycles to promote fibril formation and aggregation. Also, polyammonium substrates are able to tune the length of the overall helix assemblies and the rigidity of long oligomers. The reported data on one-turn, two-turn helices and macrocycles not only allows one to devise a model for the ion-controlled supramolecular assembly of such systems but also provides evidence that such controlled scaffolds bear promise in the design of complex systems.     

Organogelators based on TTF supramolecular assemblies: synthesis, characterization, and conductive property

A closely related family of organogelators 1-2 appended one or two electroactive tetrathiafulvalene (TTF) residues, has been designed and readily synthesized by Sonogashira reactions. These compounds can gelate a variety of organic solvents in view of multiple intermolecular interactions, and compounds 2 with two TTF subunits exhibit higher gelation ability than their corresponding 1. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) investigation of the xerogels from toluene gave a visual image showing that fibrillar aggregates are entangled in three-dimensional network structures. The columnar TTF cores stacking in the fiber, evidenced by the mixed-valence states absorption at around 2000 nm in ultraviolet-visible-near-infrared (UV-vis-NIR) spectra, provide an efficient pathway for the electron conduction. Upon oxidized by iodine, these xerogels exhibit semiconductive behaviors with moderate levels of conductivity. Additionally, the electrical conductivity of doped-xerogels 2 is 1 order of magnitude higher than that of 1 under identical conditions.