Spectroscopic Tracking of Salicylideneaniline Photocolored Crystals: An Attempt to Quantify Polymorph-Dependent Features toward Precise Structure-Function Correlation Analysis.

Three polymorphs of salicylideneaniline (SA) were prepared, and their photochromic behavior was examined using a recently developed single-crystal microscopic UV-vis spectroscopy approach. This system enabled us to acquire absorption data during the bleaching process as a function of temperature and visible light intensity. First, we demonstrated that, in contrast to the generally accepted assumption, the bleaching curves were notably influenced by the degree of photosaturation at the initial stage. By modifying our kinetic model to include the term representing the initial degree of photosaturation, we successfully obtained the kinetic parameters intrinsic to each crystal structure. Second, we further analyzed the kinetic parameters to show that the bleaching process was accelerated by visible light irradiation to a significantly higher degree than by thermal relaxation. The two bleaching-prompting effects were quantitatively compared between two photochromic polymorphs, α1 and α2; the long life of the photoproduct in α2 was attributed to efficient self-shielding from visible light irradiation enabled by its structural features. These results prompted us to reexamine the simple dualistic photochemical and thermal classification of photochromic systems and will provide a foundation for the precise structure-function analysis of crystalline materials, including SAs.

Synthesis and Properties of Salicylaldehydes Fine-Tuned by Modular Assembly using "Plug-and-Socket"-Type Extendibility.

A salicylaldehyde derivative bearing four pyridine arms, 3,5-bis(N,N-bis(2-pyridylmethyl)aminomethyl)-2,4-dihydroxybenzaldehyde (Hbpsal) as a "socket", was prepared and used to derive a series of zinc complexes with various extra anions "plugged" into their vacant site. The crystal structure and 1 H NMR spectra were noticeably influenced by the extra anions, allowing fine-tuning of the properties by "plug-and-socket"-type modification. Similar to unsubstituted salicylaldehyde, the zinc complexes reacted with primary amines to afford Schiff-base compounds. Because of the potential chirality around the coordination sphere, reaction with a chiral amine resulted in an equilibrium system between diastereomers, the potential of which as chiral sources tunable by the extra anions is discussed. Some of the complexes were further converted into zinc- or nickel-salphen (=N,N-bis(salicylidene)-1,2-phenylenediamine) complexes. The electrochemical properties of the nickel complex were slightly modified by the extra anions, whereas the photophysical properties of the zinc complex appeared unchanged.

Systematic investigations on fused π-system compounds of seven benzene rings prepared by photocyclization of diphenanthrylethenes.

We studied the photoproducts of 1-(n-phenanthryl)-2-(m-phenanthryl)ethenes (nEm; n, m = 1, 3 and 9) for understanding photocyclization patterns based on NMR spectroscopy. The crystal structures of the photoproducts were analyzed by X-ray crystallography, and the photophysical features of the photocyclized molecules were investigated based on emission and transient absorption measurements. Phenanthrene derivatives substituted at the 1- and 3-positions were prepared for synthesizing nEm by photocyclization of stilbene derivatives. We obtained four types of primary photoproducts (n@m) from the corresponding nEm. Two of them were found to have racemic molecular structures in the single crystal determined by X-ray crystallography. Besides the primary photoproducts, two types of secondary photoproducts (n@mPP) were isolated. Fluorescence quantum yields and lifetimes of the obtained photoproducts were determined in solution whereas the definite fluorescence quantum yields were obtained in the powder. Observation of the triplet-triplet absorption spectra in solution by laser photolysis techniques showed that intersystem crossing to the triplet state competes with the fluorescence process.

Spectroscopic tracking of Schiff base compounds' hydrogen bonding reorganization associated with solid-to-solid phase transition.

A series of 2,6-dihydroxynaphthalene-1-methylidene alkylamines whose alkyl chain lengths ranged from 9 to 12 was spectroscopically examined. Transmission ultraviolet-visible absorption microspectroscopy revealed that the spectra of solid thin-films of the crystalline samples showed two distinct profiles depending on polymorphs as well as on alkyl chain length. We concluded that these spectral changes occurred not because of conventional intramolecular proton transfer but because of the molecules' interactions with an external proton source, that is, the intermolecular proton transfer. The spectral changes were accompanied by changes in the intermolecular hydrogen bonding network. When a crystal of a sample compound was heated, its spectrum changed dramatically before the crystal underwent a solid-to-solid phase transition to another polymorph. We concluded that these spectral changes indicated strengthening of intermolecular hydrogen bonding or intermolecular proton transfer, which would have triggered a drastic change in the hydrogen bonding network structure.

Mutual interference between intramolecular proton transfer sites through the adjoining π-conjugated system in Schiff bases of double-headed, fused salicylaldehydes.

We synthesized two constitutionally isomeric bis(iminomethyl)-2,6-dihydroxynaphthalenes, namely, α,α-diimines 1 and ß,ß-diimines 2, which can be formally represented as fused salicylaldimines with resonance-assisted hydrogen-bonding sites. Spectroscopic data show that the OH/OH, NH/OH, and NH/NH forms of 1 were in equilibrium in solution and that the proportion of the NH-bearing tautomers increased as the solvent polarity increased. The UV spectra of thin solid films of 1 with various types of hydrogen-bonding networks differed from one another, and the spectral profiles were markedly temperature dependent, whereas the spectra of 1 in the molten state showed quite similar profiles. In contrast, 2 existed predominantly as the OH/OH form irrespective of the solvent polarity or crystal packing. Quantum chemical calculations suggest that the difference between the probabilities of intramolecular proton transfer in 1 and 2 can be explained in terms of the interplay between the resonance-assisted hydrogen-bonding sites and the adjoining π-conjugated system.

Photoinduced Crystal-to-Liquid Transition of Acylhydrazone-Based Photoswitching Molecules.

A photoinduced crystal-to-liquid transition (PCLT) behavior of new acylhydrazone derivatives (NCs) is reported. The photoswitching of the NCs was identified as a negative photochromism with a high E-to-Z conversion yield (>98%). A kinetic analysis shows a half-life of almost one month. Owing to these high photoswitching performances, we successfully isolated both E- and Z-forms, evaluated their crystal structures, and observed distinct thermal behaviors. The Z-form melts at a lower temperature than the E-form by several tens of degrees. The PCLT occurs at even lower temperatures. UV irradiation induces the E-to-Z conversion in the crystalline state, thereby inducing a eutectic melting. In addition to the PCLT, we observed a photomechanical behavior of the crystals, which suggests that the presented acylhydrazones can be new members of the photoresponsive crystalline materials.

Dry micromanipulation of supramolecular giant vesicles on a silicon substrate: highly stable hydrogen-bond-directed nanosheet membrane.

Guanosine derivative 1 forms hydrogen-bond-directed giant vesicles. On a silicon substrate, the vesicles retain their shape and internal water phase even after removal of external water under vacuum. Dry manipulation of the micrometer-sized vesicles was carried out via AFM-tip-induced partition and fusion of the vesicles. For larger vesicles (5-10 µm), external solutions were successfully injected through a microcapillary inserted into the vesicle in air.

Blue/red linear dichroic emission from a highly anisotropic crystal of triarylmethane dye conjugated with phenoxo-zinc complexes.

We have developed a novel triphenylmethane-based hexanuclear zinc complex that exhibits peculiar photochemical and photophysical properties. Upon UV irradiation, the compound turned from colorless to reddish purple, while the color of emission turned from blue to red. The color change was attributed to an oxidation of the ligand part. It was suggested that an intramolecular energy-transfer mechanism operates to give rise to the red emission. The UV treatment of a single crystal results in simultaneous emission of orthogonally polarized blue and red light. This color switching, namely linear dichroic emission was so distinct that one can recognize with by sight through optical microscope. The columnar arrangement of molecules in the crystal clearly accounts for the observed polarization of the emission.

Hydrogen-bond-directed giant unilamellar vesicles of guanosine derivative: preparation, properties, and fusion.

By mixing a small volume of THF containing guanosine derivative 1 and tetraethylenegrycol dodecyl ether (TEGDE) with water and subsequently removing TEGDE by gel permeation chromatography, micrometer-sized giant unilamellar vesicles (GUV) of 1 were successfully prepared. The vesicle membrane was a 2-D sheet assembly of thickness 2.5 nm, composed of a 2-D inter-guanine hydrogen-bond network. The GUV dispersion showed high stability because of a large negative zeta potential, which allowed repeated sedimentation and redispersion by centrifugation and subsequent gentle agitation. TEGDE-triggered fusion of GUVs took place within 350 ms, which proceeded by fusion of the vesicle membranes in contact. These unique static and dynamic properties of the GUV membrane assembled by the 2-D hydrogen-bond network are discussed.

Hydrogen-bond-directed 2-D sheet assemblies of sulfamide derivatives: formation of giant vesicles with patchwork-like surface pattern.

Sulfamide derivatives showed high ability to form hydrogen-bond-directed two-dimensional (2-D) sheet assemblies of nanometer thickness. Further, fine-tuning of the side chain structures and preparation conditions allowed for the formation of micrometer-sized giant vesicles of 4b in water by the simple injection method. IR and XRD studies indicated that 4b having tetradecyl and oxyethylene-terminated alkyl side chains formed hydrogen-bond-directed 2-D nanosheet pairs. SEM, AFM, and TEM observation of the dried vesicles revealed that the vesicle membrane was composed of several lamellar-stacked layers of 2-D nanosheets and showed a characteristic patchwork-like pattern on the surface.

Ratchet-like mechanism in a long-life photoproduct of salicylideneaniline enclathrated in a pillared-layer guanidinium disulfonate structure.

Salicylideneaniline (SA) was found to exhibit extraordinary long-life photochromism upon being included in a cavity of guanidinium organosulfonate and exhibited a lifetime of ∼30 times that of a pure SA crystal. Crystal structure analysis suggested that the sulfonate molecule in the apo-host provided a flexible cavity space that kinetically trapped SA in its photo-isomerized form, as if it was locked by a ratchet-like mechanism.

Cold Crystallization and the Molecular Structure of Imidazolium-Based Ionic Liquid Crystals with a p-Nitroazobenzene Moiety.

The cold crystallization mechanism of 1-{[4'-(4″-nitrophenylazo)phenyloxy]}hexyl-3-methyl-1H-imidazol-3-ium tetrafluoroborate ionic liquid crystal was investigated based on thermal analysis, structural analysis, infrared spectroscopy, and quantum chemical calculations. By conducting thorough structural characterization, we found that the prerequisite for cold crystallization is the irreversible molecular conformational alteration induced by the initial heating of the as-grown crystal into a smectic liquid crystal. The originally linear cation molecule bends and forms a step-stair conformation that persists throughout the subsequent heating and cooling processes as phase transition occurs from the crystal phase to the liquid crystal phase and then to the isotropic liquid phase. The formation of cold crystal occurs because of the choice of molecular stability over crystalline stability. Given the exothermic anomaly exhibited upon heating generic crystals to cold crystals, these findings demonstrate the promising potential of this ionic liquid crystal for thermal energy storage applications.

Hydrogen-bond-directed giant vesicles of guanosine derivatives in water: formation, structure, and stability.

Hydrogen-bond-directed giant supramolecular vesicles (diameter 1.20 +/- 0.30 microm (SD)) of an alkylsilylated deoxyguanosine derivative, 2a, were prepared faciley by mixing a small volume of a 2a/THF solution with water. The formation of 2-D inter-guanine hydrogen-bond networks of 2a within the vesicles was indicated by IR spectra. The vesicle solution was stable enough for more than 30 days, in a wide range of temperatures, and between pH 4 and 10 without showing lysis, fusion, precipitation, or leakage of the encapsulated fluorescent probe. In a typical micrometer-sized vesicle, a sufficiently large internal water phase for encapsulating water-soluble substances was surrounded by a multilamellar membrane 15-20 nm in thickness, which was composed of 6-9 layers of 2-D hydrogen-bond-directed sheet assemblies. AC-mode AFM observation of the vesicle on a silicon substrate further demonstrated the high stability and deformable properties of the vesicle membrane under vacuum or mechanical stress. The formation and properties of the vesicle membrane in water were analyzed from the viewpoint of the 2-D hydrogen-bond-directed sheet assemblies, and the scope of the design principle to use nonpolar soft segments as the shielding units of the hydrogen-bond networks in water is discussed.

A superelastochromic crystal.

Chromism-color changes by external stimuli-has been intensively studied to develop smart materials because of easily detectability of the stimuli by eye or common spectroscopy as color changes. Luminescent chromism has particularly attracted research interest because of its high sensitivity. The color changes typically proceed in a one-way, two-state cycle, i.e. a stimulus-induced state will restore the initial state by another stimuli. Chromic systems showing instant, biphasic color switching and spontaneous reversibility will have wider practical applicability. Here we report luminescent chromism having such characteristics shown by mechanically controllable phase transitions in a luminescent organosuperelastic crystal. In mechanochromic luminescence, superelasticity-diffusion-less plastic deformation with spontaneous shape recoverability-enables real-time, reversible, and stepless control of the abundance ratio of biphasic color emissions via a single-crystal-to-single-crystal transformation by controlling a single stimulus, force stress. The unique chromic system, referred to as superelastochromism, holds potential for realizing informative molecule-based mechanical sensing.

Experimental and theoretical studies on constitutional isomers of 2,6-dihydroxynaphthalene carbaldehydes. Effects of resonance-assisted hydrogen bonding on the electronic absorption spectra.

We prepared and characterized a series of mono- and dicarbaldehydes of 2,6-dihydroxynaphthalene that bear potential resonance-assisted hydrogen bonding (RAHB) unit(s). X-ray crystal structures of selected compounds revealed that each salicylaldehyde moiety forms an intramolecular hydrogen bond and that the introduction of formyl groups into either the alpha- or beta-position causes a considerable difference in geometry, which was interpretative from a conventional scheme of resonance hybrids including ionic state. Analyses on NMR chemical shifts suggested that the compounds in solution are present as an equilibrium mixture between closed and open forms with respect to RAHB units. Ab initio calculations indicated that the formation of an intramolecular hydrogen bond strikingly influences the aromaticity of the individual local six-membered ring of naphthalene. The trend of the change in aromaticity was analyzed in connection with the extra stabilization energy of RAHB. In the UV-vis spectra, the beta-formyl derivatives specifically showed a substantial red shift compared to alpha-formyl derivatives. The absorption features were successfully reproduced by TD-DFT calculation, and those data were consistently explained from the effects of RAHB on electronic state of the naphthalene's pi-system. Finally, we pointed out a similarity in the electronic state between RAHB-bearing molecules and cata-condensed aromatic hydrocarbons.

Development of Imidazo[1,2- a]pyridine Derivatives with an Intramolecular Hydrogen-Bonded Seven-Membered Ring Exhibiting Bright ESIPT Luminescence in the Solid State.

Imidazo[1,2- a]pyridine derivatives with different hydroxyaryl units (1-3), which could potentially form an intramolecular hydrogen-bonded seven-membered ring in either a planar or a twisted conformation, were newly developed, and the effect of conformation and steric repulsion on the excited-state intramolecular proton transfer (ESIPT) luminescence was evaluated. Among them, 1 and 2 formed an intramolecular hydrogen-bonded seven-membered ring in the crystalline state and exhibited efficient ESIPT luminescence in the solid state (quantum yield up to 0.45).

Single-crystal UV-vis spectroscopic examination of a striking odd-even effect on structure and chromic behaviour of salicylidene alkylamines.

We have found that a series of N-(5-bromosalicylidene) alkylamines exhibited distinct chromic behaviour depending on the parity of their alkyl chain length. A group with an even number of carbon atoms in the alkyl chain showed photochromism, while another group with odd number showed thermochromism.

Spontaneous ligand nitrosation and self-assembly into a pentacopper metallacrown complex.

Upon mixing acetylacetonedioxime and copper(ii) nitrate in water, the acetylacetonedioxime is spontaneously nitrosated at the central α-carbon and four of the nitrosated ligand molecules and five Cu ions self-assemble into a pentanuclear metallacrown complex, whose structure has been revealed by single crystal X-ray analysis and magnetic interactions between the Cu ions in the complex have been probed. The lability of the core Cu ion in the complex is suggested.

Nucleobase-containing gelators.

Nucleobases are nitrogenous heterocyclic compounds and have high ability to form directionally controlled multiple intermolecular interaction, i.e., in-plane multiple hydrogen-bonding interactions and stacking interactions perpendicular to the plane. Here the recent development of nucleobase-containing low molecular mass gelators in aqueous and organic systems is reviewed, and the self-assemblies of nucleobase-containing small molecules and their arrangement within the gel are discussed from the molecular, and mesoscopic to the macroscopic level in regard to becoming a macroscale three-dimensional network. Brief overview of the nucleoside-containing supramolecular materials are also presented.