Chirality in Singlet Fission: Controlling Singlet Fission in Aqueous Nanoparticles of Tetracenedicarboxylic Acid Ion Pairs.

The singlet fission characteristics of aqueous nanoparticles, self-assembled from ion pairs of tetracene dicarboxylic acid and various amines with or without chirality, are thoroughly investigated. The structure of the ammonium molecule, the counterion, is found to play a decisive role in determining the molecular orientation of the ion pairs and its regularity, spectroscopic properties, the strength of the intermolecular coupling between the tetracene chromophores, and the consequent singlet fission process. Using chiral amines has led to the formation of crystalline nanosheets and efficient singlet fission with a triplet quantum yield as high as 133% ±20% and a rate constant of 6.

Photoliquefaction and phase transition of -bisazobenzenes give molecular solar thermal fuels with a high energy density.

A series of -bisazobenzene chromophores modified with various alkoxy substituents (1; methoxy, 2; ethoxy, 3; butoxy, 4; neopentyloxy) were developed for solvent-free molecular solar thermal fuels (STFs). Compounds (,)-1-3 in the crystalline thin film state exhibited photoliquefaction, the first example of photo-liquefiable -bisazobenzenes. Meanwhile, (,)-4 did not show photoliquefaction due to the pronounced rigidity of the interdigitated molecular packing indicated by X-ray crystallography.

Far-red triplet sensitized -to- photoswitching of azobenzene in bioplastics.

We report the first example of direct far-red triplet sensitized molecular photoswitching in a condensed phase wherein a liquid azobenzene derivative (Azo1) co-assembled within a liquid surfactant-protein film undergoes triplet sensitized -to- photoswitching upon far-red/red light excitation in air. The role of triplet sensitization in photoswitching has been confirmed by quenching of sensitizer phosphorescence by -Azo1 and temperature-dependent photoswitching experiments. Herein, we demonstrate new biosustainable fabrication designs to address key challenges in solid-state photoswitching, effectively mitigating chromophore aggregation and requirement of high energy excitations by dispersing the photoswitch in the trapped liquid inside the solid framework and by shifting the action spectrum from blue-green light (450-560 nm) to the far-red/red light (740/640 nm) region.

Near-infrared vapochromism in lipid-packaged mixed-valence coordination polymers.

Reversible vapochromism in the NIR region is achieved for a mixed-valence platinum complex with lipid counterions, from which exclusion of crystallization water by organic vapor alters the lipid molecular orientation, which amplifies the information to changes in the 1D coordination structure and the electronic state.

Liquid-Based Multijunction Molecular Solar Thermal Energy Collection Device.

Photoswitchable molecules-based solar thermal energy storage system (MOST) can potentially be a route to store solar energy for future use. Herein, the use of a multijunction MOST device that combines various photoswitches with different onsets of absorption to push the efficiency limit on solar energy collection and storage is explored. With a parametric model calculation, it is shown that the efficiency limit of MOST concept can be improved from 13.

Light-Triggered, Non-Centrosymmetric Self-Assembly of Aqueous Arylazopyrazoles at the Air-Water Interface and Switching of Second-Harmonic Generation.

Trans-p-methoxy arylazopyrazole spontaneously forms non-centrosymmetric polar crystals, which reversibly undergo liquefaction upon photoisomerization to the cis-isomer. This liquid cis-isomer has a large electric dipole moment and is highly soluble in water (solubility up to ≈58 mM), which is remarkably higher than that of the trans-isomer (690 μM). Vis-light illumination of the aqueous cis-isomer generates macroscopically oriented, non-centrosymmetric crystals at the air-water interface.

Enhanced Electric Polarization and Polar Switching of Dipolar Aromatic Liquids Confined in Supramolecular Gel Networks.

Dipolar aromatic liquids confined in the interstitial domains of chiral organogels show significantly enhanced electric polarization, as compared with those of pure liquids alone or organogels formed with nonpolar liquids. Intriguingly, nitrobenzene gels showed a supramolecular polar switching phenomenon; i.e.

Liquid crystalline microspheres of azobenzene amphiphiles formed by thermally induced pH changes in binary water-hydrolytic ionic liquid media.

Anionic azobenzene-containing bilayered membranes dispersed in binary water-ionic liquid (IL) media undergo proton-responsive transformation into liquid crystalline microspheres (LCMs). This transformation was induced by protons released by the heat-induced hydrolysis of tetrafluoroborate ions in the ILs. This work demonstrates the first beneficial use of hydrolysis-susceptible ILs in chemistry.

Hierarchical Hybrid Metal-Organic Frameworks: Tuning the Visible/Near-Infrared Optical Properties by a Combination of Porphyrin and Its Isomer Units.

Hybrid metal-organic frameworks (MOFs) with core/shell-like hierarchical structure comprised of zirconium metal and porphyrin (e.g., TPP) and its isomer, N-confused porphyrin (NCP), were synthesized through a seed-mediated reaction.

Simple and Versatile Platform for Air-Tolerant Photon Upconverting Hydrogels by Biopolymer-Surfactant-Chromophore Co-assembly.

Exploration of triplet-triplet annihilation based photon upconversion (TTA-UC) in aqueous environments faces difficulty such as chromophores insolubility and deactivation of excited triplets by dissolved oxygen molecules. We propose a new strategy of biopolymer-surfactant-chromophore coassembly to overcome these issues. Air-stable TTA-UC with a high upconversion efficiency of 13.

Photoresponsive Nanosheets of Polyoxometalates Formed by Controlled Self-Assembly Pathways.

Anionic Keggin polyoxometalates (POMs) and ether linkage-enriched ammonium ions spontaneously self-assemble into rectangular ultrathin nanosheets in aqueous media. The structural flexibility of the cation is essential to form oriented nanosheets; as demonstrated by single-crystal X-ray diffraction measurements. The difference in initial conditions exerts significant influence on selecting for self-assembly pathways in the energy landscape.

Photon Upconversion and Molecular Solar Energy Storage by Maximizing the Potential of Molecular Self-Assembly.

The self-assembly of functional molecules into ordered molecular assemblies and the fulfillment of potentials unique to their nanotomesoscopic structures have been one of the central challenges in chemistry. This Feature Article provides an overview of recent progress in the field of molecular self-assembly with the focus on the triplet-triplet annihilation-based photon upconversion (TTA-UC) and supramolecular storage of photon energy. On the basis of the integration of molecular self-assembly and photon energy harvesting, triplet energy migration-based TTA-UC has been achieved in varied molecular systems.

Hierarchical Self-Assembly of Luminescent Tartrate-Bridged Chiral Binuclear Tb(III) Complexes in Ethanol.

A new family of supramolecular metalloamphiphiles carrying two metal centers is developed. They are formed by bridging two coordinatively unsaturated lipophilic Tb complexes (TbL) with chiral dicarboxylate anions. The formation of bridging coordination bonds is confirmed using UV spectroscopy, induced circular dichroism (ICD), increased luminescence intensity of TbL, and electrospray ionization mass spectrometry (ESIMS) analysis.

Ferroelectric Coordination Polymers Self-Assembled from Mesogenic Zinc(II) Porphyrin and Dipolar Bridging Ligands.

A new class of ferroelectric coordination-based polymers has been developed by the self-assembly of lipophilic zinc porphyrin (ZnP) and ditopic bridging ligands. The ligands contain dipolar benzothiadiazole or fluorobenzene units, which are axially coordinated to ZnP with the dipole moments oriented perpendicular to the coordination axes. The coordination-based polymers show ferroelectric characteristics in the liquid crystalline state, as revealed by distinctive hysteresis in the polarization-electric field (P-E) loops and inversion current peaks in current-voltage (I-V) loops.

Photoliquefiable ionic crystals: a phase crossover approach for photon energy storage materials with functional multiplicity.

Ionic crystals (ICs) of the azobenzene derivatives show photoinduced IC-ionic liquid (IL) phase transition (photoliquefaction) upon UV-irradiation, and the resulting cis-azobenzene ILs are reversibly photocrystallized by illumination with visible light. The photoliquefaction of ICs is accompanied by a significant increase in ionic conductivity at ambient temperature. The photoliquefaction also brings the azobenzene ICs further significance as photon energy storage materials.

A liquid azobenzene derivative as a solvent-free solar thermal fuel.

A liquid solar thermal fuel is developed; a low-molecular weight liquid trans-azobenzene derivative shows facile photoisomerization to the higher-energy cis-isomer in neat condition so that a high volumetric energy density is achieved. Shear viscosity measurements for each isomer liquid unveiled transitions from non-Newtonian to Newtonian fluids.

Self-assembly of azobenzene bilayer membranes in binary ionic liquid-water nanostructured media.

Anionic azobenzene-containing amphiphile 1 (sodium 4-[4-(N-methyl-N-dodecylamino)phenylazo]benzenesulfonate) forms ordered bilayer membranes in binary ionic liquid (1-ethyl-3-methylimidazolium ethyl sulfate, [C2mim][C2OSO3])-water mixtures. The binary [C2mim][C2OSO3]-water mixture is macroscopically homogeneous at any mixing ratio; however, it possesses fluctuating nanodomains of [C2mim][C2OSO3] molecules as observed by dynamic light scattering (DLS). These nanodomains show reversible heat-induced mixing behavior with water.

Controlled self-assembly and luminescence characteristics of Eu(III) complexes in binary aqueous/organic media.

Luminescence of sodium tetrakis(naphthoyl trifluoroacetonato) europium(III) (Na[Eu(nta)4]) in binary aqueous-ethanol media is quenched continuously with an increase in the water content, which is ascribed to commonly observed relaxation of photoexcited lanthanide complexes through vibrational coupling with coordinating water. Meanwhile, replacement of sodium ion with an ammonium amphiphile 1 gives a lipid complex 1[Eu(nta)4] which shows distinct changes: its luminescence quantum yield Φ is remarkably increased to ~0.6 above the water content of ~60 vol.

Biopolymer-encapsulated protein microcapsules spontaneously formed at the ionic liquid-water interface.

Aqueous microdroplets introduced in ionic liquids (ILs) provide unique interfaces where surface-modified protein microcapsules are spontaneously formed at systemic temperature. The susceptibility of proteins to form microcapsules at the water-IL microinterface depends on protein species and is related to the number of charged residues exhibited on protein surfaces. When both of the capsule-forming (host) proteins and guests biopolymers such as nucleic acids or enzymes are introduced in the aqueous microdroplets, microcapsules are formed selectively from host proteins while the guest biopolymers remain encapsulated in the aqueous pool.

Converting molecular information of redox coenzymes via self-assembly.

β-Nicotinamide adenine dinucleotide (NAD(+)) and its reduced form NADH specifically interact with a cyanine dye in aqueous media, giving distinct spectral and nanostructural characteristics to which molecular information of constituent coenzymes are converted via self-assembly.

Ionic liquids induced structural changes of bovine serum albumin in aqueous media: a detailed physicochemical and spectroscopic study.

Structural changes of a globular protein, bovine serum albumin (BSA), as a consequence of interaction with the surface active ionic liquids (ILs)-3-methyl-1-octylimidazolium chloride, [C(8)mim][Cl], and 1-butyl-3-methylimidazolium octylsulfate, [C(4)mim][C(8)OSO(3)]-have been investigated using various physicochemical and spectroscopic techniques such as tensiometry, conductometry, steady-state fluorescence, far-UV circular dichroism spectroscopy (CD), and dynamic light scattering (DLS). The interactional behavior of ILs (monomers and self-assembled structures) toward BSA in different IL concentration regimes at the air/solution interface as well as in the bulk is investigated and discussed depending upon the nature of ions of ILs. CD combined with the steady state fluorescence spectroscopy provided valuable insights into the unfolding of BSA as a consequence of IL binding.

Conversion of molecular information by luminescent nanointerface self-assembled from amphiphilic Tb(III) complexes.

A novel amphiphilic Tb(3+) complex (TbL(+)) having anionic bis(pyridine) arms and a hydrophobic alkyl chain is developed. It spontaneously self-assembles in water and gives stable vesicles that show sensitized luminescence of Tb(3+) ions at neutral pH. This TbL(+) complex is designed to show coordinative unsaturation, i.

Spatially controlled self-assembly of gold nanoparticles encased in alpha-helical polypeptide nanospheres.

Gold nanoparticles (Au-NPs) are encased in aqueous nanospheres of alpha-helical poly(gamma-benzyl L-glutamate)s (PBLG, number average degree of polymerization: n = 32), with spatially controlled self-assembly structures of solid core-shell nanospheres or double-layered hollow nanocapsules.