Chiral Induction of a Tetrakis(porphyrin) in Various Chiral Solvents.

Non-covalent interactions offer an alternative way for developing stimulus-responsive materials such as sensors, machines, and drug-delivery systems. We recently reported that a urethane-equipped tetrakis(porphyrin) forms one-handed helical supramolecular polymers in solution in response to chirality of chiral solvents. Conformational changes in helical sense were detected using circular dichroism (CD) spectroscopy, which showed that the tetrakis(porphyrin) can possibly be used as a sensor for determining the enantiomeric excess of a chiral analyte.

Controlled Helical Organization in Supramolecular Polymers of Pseudo-Macrocyclic Tetrakisporphyrins.

Tetrakisporphyrin monomers with amino acid side chains at each end form intramolecular antiparallel hydrogen-bonds to adopt chirally twisted pseudo-macrocyclic structures that result in right-handed and left-handed (P)- and (M)-conformations. The pseudo-macrocyclic tetrakisporphyrin monomers self-assembled to form supramolecular helical pseudo-polycatenane polymers via head-to-head complementary dimerization of the bisporphyrin cleft units in an isodesmic manner. The formation of one-handed supramolecular helical pseudo-polycatenane polymers was confirmed by circular dichroism (CD) spectroscopy.

Latent porosity of planar tris(phenylisoxazolyl)benzene.

Interest in developing separation systems for chemical entities based on crystalline molecules has provided momentum for the fabrication of synthetic porous materials showing selectivity in molecular encapsulation, such as metal-organic frameworks, covalent organic frameworks, hydrogen-bonded organic frameworks, zeolites, and macrocyclic molecular crystals. Among these, macrocyclic molecular crystals have generated renewed interest for use in separation systems. Selective encapsulation relies on the sizes, shapes, and dimensions of the pores present in the macrocyclic cavities; thus, nonmacrocyclic molecular crystals with high selectivity for molecular encapsulation via porosity-without-pore behaviors have not been studied.

Supramolecular chiral sensing by supramolecular helical polymers.

A tetrakis(porphyrin) with branched side chains self-assembled to form supramolecular helical polymers both in solution and in the solid state. The helicity of the supramolecular polymers was determined by the chirality of solvent molecules, which permitted the polymer chains to be used in chiral sensing.

Lanthanide and Actinide Ion Complexes Containing Organic Ligands Investigated by Surface-Enhanced Infrared Absorption Spectroscopy.

A new technique, surface-enhanced infrared absorption (SEIRA) spectroscopy, was used for the structural investigation of lanthanide (Ln) and actinide (An) complexes containing organic ligands. We synthesized thiol derivatives of organic ligands with coordination sites similar to those of 2-[-methyl--hexanethiol-amino]-2-oxoethoxy-[,-diethyl]-acetamide [diglycolamide (DGA)], Cyanex-272, and ,,,-tetrakis(2-pyridinylmethyl)-1,2-ethanediamine (TPEN), which have been used for separating Ln and An through solvent extraction. These ligands were attached on a gold surface deposited on an Si prism through S-Au covalent bonds; the gold surface enhanced the IR absorption intensity of the ligands.

Self-assembly of neutral platinum complexes controlled by thermal inputs.

In this report, we describe the self-assembly behavior of neutral platinum complexes in toluene. The platinum complexes were seen to form two different types of assemblies depending on the preparation temperature.

Supramolecular Ensembles Formed via Calix[5]arene-Fullerene Host-Guest Interactions.

This Review introduces the research directions for the synthesis of supramolecular fullerene polymers. First, the discovery of host-guest complexes of pristine fullerenes is briefly outlined. We focus on progress in supramolecular fullerene polymers directed by the use of calix[5]arene-fullerene interactions, which comprise linear, networked, helical arrays of fullerenes in supramolecular ensembles.

Polymerization of a biscalix[5]arene derivative.

Recent decades have seen an increased interest in the preparation of polymers possessing host or guest moieties as the end group, which has enabled new polymeric materials such as self-healable, shape-memory, and stimuli-responsive materials. Such polymers are commonly synthesized by tethering the host or guest moieties to polymers. On the other hand, there are limited reports demonstrating the preparation of host- or guest-appended polymers by directly polymerizing the corresponding host- or guest-appended monomers, which is valuable for easy access to diverse polymers from single molecular species.

Self-sorting behavior in supramolecular fullerene polymerization directed by host-guest complexation between calix[5]arene and C.

We describe self-sorting supramolecular polymerization that uses chiral calix[5]arene hosts and a dumbbell-shaped fullerene guest. In a solution containing the racemic host and the guest, the ()-host and the ()-host preferably formed their homomeric complexes to form helical supramolecular fullerene polymers in a self-sorting manner. The self-sorting behavior has been studied using diffusion-ordered H NMR (DOSY) and circular dichroism (CD) studies.

Solvent-directed formation of helically twisted stacking constructs via self-assembly of tris(phenylisoxazolyl)benzene dimers.

Ureido-pyrimidinone (UPy)-appended tris(phenylisoxazolyl)benzenes were synthesized. The UPy moieties of the tris(phenylisoxazolyl)benzenes stably formed self-complementary dimers in solution. The dimers self-assembled to form helically twisted stacking constructs in a process driven by π-π stacking interactions of UPy dimer moieties and dipole-dipole interactions of isoxazole units.

Gas-Phase UV Spectroscopy of Chemical Intermediates Produced in Solution: Oxidation Reactions of Phenylhydrazines by DDQ.

In this study, we demonstrated cold gas-phase spectroscopy of chemical intermediates produced in solution. Herein, we combined an electrospray ion source with a T-shaped solution mixer for introducing chemical intermediates in solution into the gas phase. Specifically, the oxidation reaction of 2-(4-nitrophenyl)hydrazinecarboxaldehyde (NHCA) by 2,3-dichloro-5,6-dicyano--benzoquinone (DDQ) was initiated by mixing the methanol solutions of NHCA and DDQ in the T-shaped mixer, and the chemical species were injected into the vacuum apparatus for ultraviolet photodissociation (UVPD) spectroscopy.

Negative Cooperativity in Guest Binding of a Ditopic Self-Folding Biscavitand.

A brand-new self-folding biscavitand was synthesized from a feet-to-feet-connected bisresorcinarene. The X-ray crystal structure of the biscaivtand showed that the two cavities are tightly connected with four butylene linkages. The conformationally coupled two cavities accommodated two cationic guests, showing a homotropic negative cooperativity in nonpolar solvents (toluene and chloroform).

Supramolecular Fluorescent Sensors: An Historical Overview and Update.

Since as early as 1867, molecular sensors have been recognized as being intelligent "devices" capable of addressing a variety of issues related to our environment and health (e.g., the detection of toxic pollutants or disease-related biomarkers).

Self-assembly of neutral platinum complexes possessing chiral hydrophilic TEG chains.

Neutral platinum complexes that possess chiral triethylene glycol (TEG) moieties were synthesized. The platinum complexes formed helically twisted stacked assemblies in chloroform and toluene, which were studied by H NMR, UV/vis spectroscopy, and emission spectroscopy. On the other hand, emissive micellar aggregates were observed in a THF/water mixed solvent.

Self-Assembling Behavior and Chiroptical Properties of Carbazole-Cored Phenyl Isoxazolyl Benzenes.

Carbazole-cored phenyl isoxazolyl benzenes possessing chiral moieties were synthesized. The molecules self-assembled to form stacked supramolecular assemblies in an isodesmic fashion in chloroform, whereas the molecules preferably assembled in a cooperative fashion in methylcyclohexane (MCH), which was determined by spectroscopic methods, including UV-vis absorption, fluorescence, and H NMR spectroscopy. Clear nucleation and elongation processes were observed in the plot of the degree of aggregation (α) against temperature, which allowed us to determine the elongation temperature (), the enthalpic gain in the elongation process (Δ), the equilibrium constant between nucleation and elongation (), and the degree of polymerization at the elongation temperature ([()]).

Helically Organized Fullerene Array in a Supramolecular Polymer Main Chain.

To date, supramolecular chemistry techniques have been applied to fullerene polymer synthesis, enabling the development of main-chain fullerene polymers whose primary structure is well regulated, including linear, dendritic, and net-like fullerene arrays. These research achievements have led to an intriguing scientific challenge to create main-chain fullerene polymers with higher structural regulation. Here, we report the fabrication of a helically organized fullerene array based on the supramolecular polymerization of chiral ditopic tetrakiscalix[5]arene hosts and a dumbbell-shaped fullerene.

A Light-Harvesting/Charge-Separation Model with Energy Gradient Made of Assemblies of meta-Pyridyl Zinc Porphyrins.

Self-assembly of porphyrins is a fascinating topic, not only for mimicking chlorophyll assemblies in photosynthetic organisms, but also for the potential of creating molecular-level devices. Herein, zinc porphyrin derivatives bearing a meta-pyridyl group at the meso position were prepared and their assemblies studied in chloroform. Among the porphyrins studied, one with a carbamoylpyridyl moiety gave a distinct H NMR spectrum in CDCl , which allowed the supramolecular structure in solution to be probed in detail.

Self-Healing Supramolecular Materials Constructed by Copolymerization via Molecular Recognition of Cavitand-Based Coordination Capsules.

The repeating guest units of poly-(R)-2 were selectively encapsulated by the self-assembled capsule poly-1 possessing eight polymer side chains to form the supramolecular graft polymer (poly-1) ⋅poly-(R)-2. The encapsulation of the guest units was confirmed by H NMR spectroscopy and the DOSY technique. The hydrodynamic radius of the graft polymer structure was greatly increased upon the complexation of poly-1.

A dual redox-responsive supramolecular polymer driven by molecular recognition between bisporphyrin and trinitrofluorenone.

A dual redox-responsive supramolecular polymer driven by molecular recognition between bisporphyrin (bisPor) and trinitrofluorenone (TNF) has been developed. The supramolecular polymer was degraded into monomers in response to both oxidation and reduction stimuli.

Helicity of a polyacetylene directed by molecular recognition of biscalixarene and fullerene.

Chiral biscalixarenes and a C60-appended polyphenylacetylene have been synthesized. The chiral biscalixarene encapsulated the C60 unit of the phenylpolyacetylene, which induced the preferred helicity of the polyacetylene.

Columnar Organization of Carbo[5]helicene Directed by Peripheral Steric Perturbation.

Three carbo[5]helicenes ([5]CHs) containing benzylmaleimide groups displayed columnar stacked organizations, including dislocated, parallel, and alternating ()- and ()-helix molecular arrangements in the solid state. The peripheral benzyl groups resulted in very small steric interactions that are responsible for the formation of columnar stacked arrangements in the crystalline state.

AIE-active micelles formed by self-assembly of an amphiphilic platinum complex possessing isoxazole moieties.

An increased interest in the use of platinum complex based luminescent micelles for imaging biological tissues has emerged in recent years due to their low cytotoxicity, synthetic flexibility, photostability, and high emission efficiency. Here, we report a luminescent micelle that is prepared through the self-assembly of an amphiphilic, neutral Pt(ii) complex with isoxazole moieties in THF/water on account of its aggregation-induced emission (AIE) property.

Helical assembly of a dithienogermole exhibiting switchable circularly polarized luminescence.

Dithienogermole derivatives S- and R-1 possessing phenylisoxazoles and chiral side chains were synthesized. The helical assembly of 1 in methylcyclohexane exhibited circularly polarized luminescence (CPL). The CPL signals of the assembly in the elongation regime were inverted with respect to those in the nucleation regime.

Supramolecular Properties of a Monocarboxylic Acid-Functionalized "Texas-Sized" Molecular Box.

A new carboxylic acid-functionalized "Texas-sized" molecular box TxSB-COH has been prepared by combining two separate building blocks via an iodide-catalyzed macrocyclization reaction. A single-crystal X-ray diffraction analysis revealed a paired "clip-like" dimer in the solid state. Concentration-dependent behavior is seen for samples of TxSB-COH as prepared, as inferred from H NMR spectroscopic studies carried out in DMSO- d.

Control over multiple molecular states with directional changes driven by molecular recognition.

Recently, ligand-metal coordination, stimuli-responsive covalent bonds, and mechanically interlinked molecular constructs have been used to create systems with a large number of accessible structural states. However, accessing a multiplicity of states in sequence from more than one direction and doing so without the need for external energetic inputs remain as unmet challenges, as does the use of relatively weak noncovalent interactions to stabilize the underlying forms. Here we report a system based on a bispyridine-substituted calix[4]pyrrole that allows access to six different discrete states with directional control via the combined use of metal-based self-assembly and molecular recognition.