A Concise Route to Keto-Bridged Polyphenols by Photo-Fries Rearrangement in Flow.

Described is a new synthetic route to bis(2-hydroxy-3,5-di-t-butylphenyl)methanone and its derivatives. The combined esterification/photo-Fries rearrangement approach enables a modular preparation of keto-bridged polyphenols. This protecting group-free process is highly atom- and step-economic, and a scalable production was easily achieved in the continuous-flow mode.

Missing Piece in Colloidal Stability─Morphological Factor of Hydrophobic Nanoparticles.

Hydrophobic nanoparticles (NPs) in water were considered unstable because they lack the repulsive electrostatic interaction and steric effect to prevent aggregation. In this study, porous hydrophobic NPs of two star-shaped giant molecules, POSS-(R)8, were found to be stable in water and able to retain their kinetic stability in a wide range of temperatures, pH values, and ionic strengths. Unlike the solid hydrophobic NPs that aggregate even with the negative zeta potential (ζ) induced by surface-structured hydrogen-bonded (SHB) water, the porous morphology of POSS-(R)8 NPs reduces the entropically driven hydrophobic effect to prevent aggregation. With the porous morphology, the hydrophobic NPs are stable without the hydrophilic or charged surface functional groups and demonstrate good encapsulation capability. The morphological factor of colloids is thus one of the missing pieces in the theory of colloidal stability that extends our understanding of colloidal science.

Benzimidazolone-Dioxazine Pigments-Based Conjugated Polymers for Organic Field-Effect Transistor.

Molecules based on benzimidazolone-dioxazine are known as blue/violet pigments and have been commercialized for decades. However, unfavorable solubility limits the application of these structures as building blocks of conjugated polymers despite their low band gaps. Herein, a series of donor-acceptor conjugated polymers containing soluble benzimidazolone-dioxazine structures as the acceptors and oligothiophene as donors are synthesized and investigated. With increasing numbers of thiophene rings, the steric hindrance diminishes and high molecular weight polymers can be achieved, leading to an improved performance in organic field effect transistor devices. The hole mobility of polymers with three to six thiophene units is in the order of 10-1 cm2 V-1 s -1 . Among all the polymers, polymer P3 with three thiophene units between benzimidazolone-dioxazine structures shows the best hole mobility of 0.4 cm2 V-1 s -1 . Grazing-incidence wide-angle X-ray scattering results reveal that the high mobility of organic field-effect transistors (OFETs) can be accredited by matched donor-acceptor packing in the solid thin films.

Connecting Molecular and Supramolecular Shapeshifting by the Ostwald's Nucleation Stages of a Star Giant Molecule.

The shapeshifting behavior for synthetic matters was found at either the molecular or supramolecular level, but the connection between shapeshifting at the two hierarchical levels remains missing. In this study, an 8-arm star giant molecule, NPOSS, was synthesized to connect the molecular and supramolecular shapeshifting. Controlling the conditions of bulk self-assembly allowed us to bring NPOSS into three different Ostwald's stages of nucleation. The high conformational flexibility of NPOSS facilitates molecular shapeshifting and allows NPOSS to take the discotic, rod-like and star-like geometries in different Ostwald's stages. Simultaneous changes in the supramolecular scaffolds were observed as the discotic, rod-like and star-like NPOSS molecules self-assembled into the supramolecular scaffolds of 1D columns, 2D lamellae, and 3D networks, respectively. These changes in the hierarchical structures also affect the CO2 affinity of NPOSS. Therefore, the connection between the molecular/supramolecular shapeshifting and the structure-driven property changes of NPOSS were established by taking advantage of the high conformational freedom of the 8-arm star giant molecule and its diverse self-assembly pathways leading to the different Ostwald's stages.

Dual-Axis Alignment of Bulk Artificial Water Channels by Directional Water-Induced Self-Assembly.

Approaching single-crystal-like morphology has always been important in driving materials toward their optimal properties. With only orientational order, liquid crystal (LC) materials require dual-axis orientational control to optimize their structural order in the bulk phase. However, current external guiding fields such as electrical, magnetic, and mechanical guiding fields are less effective in aligning amphiphilic LCs. In this study, water is developed as an excellent structural stabilizer and orientation-directing agent of an amphiphilic discotic molecule (AD) in the water-induced self-assembly (WISA) process. Thermal analysis and structural characterization results show that water increases the stability and domain sizes of the hexagonal columnar (Colh) phase of the AD by co-assembling with the ADs to form bulk artificial water channels (AWCs). Moreover, through control over the nucleation conditions (degree of supercooling and location of nucleation), dual-axis alignment in both the planar and vertical growth of the AWCs is achieved by applying water as the guiding field in the directional WISA. With precise control over the hierarchical structures, the bulk AWC array of the AD delivers excellent salt rejection properties and water permeability. Considering that all the amphiphilic LCs have hydrophilic segments, these new roles of water in the WISA process could launch the further development of functional amphiphilic LCs by providing a dynamic interaction and a readily available guiding field.

Aqueous Self-Assembly of Hydrophobic Molecules Influenced by the Molecular Geometry.

Water, in addition to acting as a solvent, plays a constructional role in aqueous self-assembly. The hydrophobic molecule of POSS-PDI-POSS (POSS = polyhedral oligomeric silsesquioxanes, PDI = perylene diimide) has a shape anisotropy in which POSS is a ball-like bulky group and PDI is a flat aromatic group. The self-assembly of this molecule in water created assemblies with inner spaces due to the steric effect, which suppressed aromatic interactions of PDI and trapped water for the colloidal stability. By replacing POSS with dodecyl (C12), C12-PDI-C12 aggregated with extended aromatic interaction of PDI and less inner water. The resulting aggregates tended to agglomerate and precipitate. This discovery extended the scope of aqueous self-assembly by using the building blocks without amphiphilicity and created knowledge for biophysics.

Damp heat-stable perovskite solar cells with tailored-dimensionality 2D/3D heterojunctions.

If perovskite solar cells (PSCs) with high power conversion efficiencies (PCEs) are to be commercialized, they must achieve long-term stability, which is usually assessed with accelerated degradation tests. One of the persistent obstacles for PSCs has been successfully passing the damp-heat test (85°C and 85% relative humidity), which is the standard for verifying the stability of commercial photovoltaic (PV) modules. We fabricated damp heat-stable PSCs by tailoring the dimensional fragments of two-dimensional perovskite layers formed at room temperature with oleylammonium iodide molecules; these layers passivate the perovskite surface at the electron-selective contact. The resulting inverted PSCs deliver a 24.3% PCE and retain >95% of their initial value after >1000 hours at damp-heat test conditions, thereby meeting one of the critical industrial stability standards for PV modules.

Chiral Silica with Preferred-Handed Helical Structure via Chiral Transfer.

A strategy to obtain chiral silica using an achiral stereoregular polymer with polyhedral oligomeric silsesquioxane (POSS) side chains is described herein. The preferred helical conformation of the POSS-containing polymer could be achieved by mixing isotactic polymethacrylate-functionalized POSS (it-PMAPOSS) and a chiral dopant. The array structure of POSS molecules, which are placed along the helical conformation, is memorized even after removing the chiral dopant at high temperatures, leading to a chiral silica compound with exclusive optical activity after calcination.

Tailoring Photophysical Properties of Diketopyrrolopyrrole Small Molecules with Electron-Withdrawing Moieties for Efficient Solar Steam Generation.

The development of photothermal materials (PTMs) for solar steam generation (SSG) has gained tremendous attention in response to the global clean water scarcity issue. However, the investigation in employing organic small-molecule PTMs for SSG applications is rarely found due to their narrow optical absorption range to harvest solar energy and insufficient photostability for long-term use. Herein, we employ a diketopyrrolopyrrole (DPP) core unit together with electron-withdrawing (EW) endcaps and siloxane side chains to introduce stronger intramolecular charge transfer (ICT) characteristics as well as the hydrophobic character. The enhanced ICT characteristics of DPP derivatives render a broad optical absorption range, less emission, and a high nonradiative decay rate for efficient solar energy harvesting and photothermal effects. Meanwhile, the hydrophobic nature of these DPP derivatives allows the facile fabrication of novel Janus photothermal membranes for effective water vaporization and solar-to-vapor conversion efficiency. By embedding DPP derivatives to the SSG device, we showed that the solar-to-vapor efficiency can reach up to 71.8% under relatively low visible light power (∼700 W m-2), which is, on average, 2.66 times higher than that of bulk water of similar dimension. Moreover, this report demonstrates the great potential of conjugated small molecules for photothermal applications, owing to their versatility and flexibility in structural engineering and its diminishing radiative decay properties. This may inspire more innovation and advancement in SSG applications.

Water-Induced Self-Assembly of Amphiphilic Discotic Molecules for Adaptive Artificial Water Channels.

Inspired by the induced-fit mechanism in nature, we developed the process of water-induced self-assembly (WISA) to make water an active substrate that regulates the self-assembly and function of amphiphilic discotic molecules (ADMs). The ADM is an isotropic liquid that self-assembles only when in contact with water. Characterization results indicate that water fits into the hydrophilic core of the ADMs and induces the formation of a hexagonal columnar phase (Colh), where each column contains a hydrated artificial water channel (AWC). The hydrated AWCs are adaptive rather than static; the dynamic incorporation/removal of water results in the reversible assembly/disassembly of the adaptive AWCs (aAWCs). Furthermore, its dynamic characteristics can enable water to act as an orientation-directional guest molecule that controls the growth direction of the aAWCs. Well-aligned aAWC arrays that showed the ability of water transport were obtained via a "directional WISA" method. In WISA, water thus governs the supramolecular chemistry and function of synthetic molecules as it does with natural materials. By making water an active component in adaptive chemistry and enabling host molecules to dynamically interact with water, this adaptive aquatic material may motivate the development of synthetic molecules further toward biomaterials.

Host-guest chemistry of giant molecular shape amphiphiles based on POSS-PDI conjugates.

Giant shape amphiphiles (GSA) are giant molecules made with nano-building blocks that have distinct shapes. The incompatible packing behaviors of the nano-building blocks of GSA could create cavities within certain conformers of the GSA, but the host-guest chemistry of GSA has not been explored yet. In this study, POSS-PDI-POSS (PPP), which is made by connecting two nano-cubes, isobutyl-polyhedral oligomeric silsesquioxanes (POSS), to a conjugated π-conjugated core, perylene diimide (PDI), is demonstrated as a novel acyclic synthetic host. In its bent conformer, PPP shows a cavity next to its PDI core. Via forming host-guest complexes with π-conjugated guests such as pyrene and perylene, PPP is found to transform from the bent-conformer into the extended-conformer, creating the steric features to accommodate guest molecules. Subsequent thermal annealing of the host-guest complexes removes the π-conjugated guests and restores the bent conformation and photophysical properties of PPP, which verifies that PPP, as a novel acyclic host, is capable of dynamic host-guest assembly. Moreover, the results prove that cavities at the molecular level can be created by connecting nano-building blocks with distinct shapes. This finding may inspire developments in the host-guest chemistry of GSA and nanomaterial innovation.

Adaptive molecular quaternary clips made with pyrene functionalized polyhedral oligomeric silsesquioxane.

Evolving synthetic molecules toward complex structures is a major goal in supramolecular chemistry. Increasing the number of clips in a unimolecular multi-clip (UMC), although vital to elevate the complexity of supramolecular architectures, often prevents the UMC from forming host-guest complexes in the bulk phase. To overcome this difficulty, adaptive chemistry was applied to develop a novel adaptive unimolecular quaternary clip (Q-clip). The Q-clip is intrinsically amorphous, but self-organizes with exclusively 4 eq. of allosteric activators (NDI) to form the Q-clip : NDI4 complexes and a supramolecular lamellar structure in the bulk. The adaptive assembly is fast and allows us to locate the adaptive assembly area of Q-clip : NDI4 complexes in the amorphous Q-clip film. Our results provide new insights into the design of adaptive UMCs for the evolution toward complex structures and supramolecular functional materials.

Vesicular Membrane with Structured Interstitial Water.

Self-assembled vesicles with structured (tetrahedral order with strong hydrogen bonds) interstitial water are reported. The vesicles, known as MCsome, are assembled from metal carbonyl compounds, FpR (Fp = (Cp)Fe(PPh3)(CO)(CO-), Cp = cyclopentadiene, R = C3Bithiophene, C6Pyrene or C6) with the Fp heads exposed to water. The R groups are surrounded by the interstitial water with the hydrogen bonding strength variable depending on the hydrophobicity of R groups. The structure of the interstitial water is responsible for the integrity of the membrane and swelling behavior of the vesicles. This constructional role of water opens new concepts for the creation of aqueous assemblies with water-mediated functions.

Influence of Molecular Symmetry and Terminal Substituents on the Morphology and OFET Characteristics of S,N-Heteropentacenes.

Many heteroacenes have been extensively studied to improve device performances; however, the morphological effects stemmed from the chemical modification on a multiscale remain less explored. In this research, five axisymmetric S,N-heteropentacenes (DTPT, DTPT-Ph, DTPT-CN, DTPT-PYCN, and DTPT-BTCN) are studied to reveal the influences of molecular symmetry and end-capping substituents on the structure-property relationship, the thermal stability, crystallization behavior, film morphology, and OFET performance. Phase behavior was probed by differential scanning calorimetry (DSC), while the quality of the crystal array and structural details was investigated by optical microscopy (OM) and grazing-incidence wide-angle X-ray scattering (GIWAXS). The analytic results reveal that (1) the parent axisymmetric S,N-heteropentacene, DTPT, is hard to crystallize, which hinders the preparation of high-quality crystal arrays for the OFET application. (2) The incorporation of π-conjugated electron-withdrawing (π-EW) endcaps that provide extended conjugation length and enhanced molecular polarity is required to form oriented crystal arrays to deliver reasonable OFET characteristics. (3) The π-EW endcaps with conformational freedom, such as -BTCN, due to the asymmetric feature of benzothiadiazole (BT), can hinder bulk phase crystallization and cause conformational disorder in the crystal array. Hence, the tradeoff of introducing the end-substituents to reinforce the poor crystalline nature of S,N-heteroacenes should be carefully considered.

Solution-Processable Quinoidal Dithioalkylterthiophene-Based Small Molecules Pseudo-Pentathienoacenes via an Intramolecular S···S Lock for High-Performance n-Type Organic Field-Effect Transistors.

A new organic small-molecule family comprising tetracyanoquinodimethane-substituted quinoidal dithioalky(SR)terthiophenes (DSTQs) (DSTQ-6 (1); SR = SC6H13, DSTQ-10 (2); SR = SC10H21, DSTQ-14 (3); SR = SC10H21) was synthesized and contrasted with a nonthioalkylated analogue (DRTQ-14 (4); R = C14H29). The physical, electrochemical, and electrical properties of these new compounds are thoroughly investigated. Optimized geometries obtained from density functional theory calculations and single-crystal X-ray diffraction reveal the planarity of the SR-containing DSTQ core. DSTQs pack in a slipped π-π stacked two-dimensional arrangement, with a short intermolecular stacking distance of 3.55 Å and short intermolecular S···N contacts of 3.56 Å. Thin-film morphological analysis by grazing incident X-ray diffraction reveals that all DSTQ molecules are packed in an edge-on fashion on the substrate. The favorable molecular packing, the high core planarity, and very low lowest unoccupied molecular orbital (LUMO) energy level (-4.2 eV) suggest that DSTQs could be electron-transporting semiconductors. Organic field-effect transistors based on solution-sheared DSTQ-14 exhibit the highest electron mobility of 0.77 cm2 V-1 s-1 with good ambient stability, which is the highest value reported to date for such a solution process terthiophene-based small molecular semiconductor. These results demonstrate that the device performance of solution-sheared DSTQs can be improved by side chain engineering.

Hydrogen Bonding-Induced H-Aggregation for Fluorescence Turn-On of the GFP Chromophore: Supramolecular Structural Rigidity.

To turn on the fluorescence of the native green fluorescence protein (GFP) chromophore, 4-hydroxybenzylidene-dimethylimidazolinone (HBDI), in an artificial supramolecular system has been a challenging task, because it requires high local environmental rigidity. This work shows that the formation of H-aggregates of an HBDI-containing organogelator results in two orders of magnitude fluorescence enhancement (Φf =2.9 vs. 0.02 %), in which the inter-HBDI OH⋅⋅⋅OH H-bonds play a crucial role. The aggregation-induced fluorescence enhancement of HBDI has important implications on the origin of the high fluorescence quantum efficiency of HBDI in the GFP ß-barrel and on the supramolecular strategy for a full fluorescence recovery of HBDI. These results reveal a new approach to designing rigid chromophore aggregates for high-performance optoelectronic properties.

Heat Transfer of Semicrystalline Nylon Nanofibers.

Polymers are generally regarded as thermal insulators. The efficient heat transfer observed in the low-dimensional polymers in the literature mainly result from the larger crystallinity or improved polymer chain orientation in the low-dimensional polymers. However, the role of the amorphous domain on heat transfer in polymers remains unexplored. In this work, we report that the semicrystalline nylon polymer nanofibers can exhibit a very large thermal conductivity of 59.1 ± 3.1 W m-1 K-1 and the heat transfer in the semicrystalline polymer nanofibers was time-dependent. The thermal conductivity of the nanofibers could be modulated to span 3 orders of magnitude from being nearly insulated (∼0.27 ± 0.02 W m-1 K-1) to being highly thermal conductive after annealing (∼59.1 ± 3.1 W m-1 K-1). The time-dependent thermal conductivity was observed at a temperature lower than the gamma transition temperature of the polymer and was a result of the physical aging of the semicrystalline polymer. A phenomenological model was adopted to explain the time-dependent heat transfer of the semicrystalline nanofibers. The physical aging reduced the configuration disorder in the polymer and caused the heat transfer of the semicrystalline polymer to increase during the annealing process.

n-Type Thin-Film Transistors Based on Diketopyrrolopyrrole Derivatives: Role of Siloxane Side Chains and Electron-Withdrawing Substituents.

The physical properties, packing, morphology, and semiconducting performance of a planar π-conjugated system can be effectively modified by introducing side chains and substituent groups, both of which can be complementary to the π framework in changing the intermolecular association, frontier molecular orbital energy, optical band gap, and others. We herein show that installation of end-capped electron-withdrawing groups (EWGs), such as dicyanovinyl (-DCV), 3-ethylrhodanine (-RD), and 2-(3-oxo-indan-1-ylidene)-malononitrile (-INCN), together with siloxane side chains to the backbones of dithienyldiketopyrrolopyrrole (DPPT), such as DPPT-Si-DCV, DPPT-Si-RD, and DPPT-Si-INCN, can greatly improve its solubility, air stability, and film morphology to serve as an n-channel in thin-film transistor fabrication. The EWGs attached to the DPPT core narrowed the optical band gap (Egopt) and changed the highest occupied molecular orbital and the lowest unoccupied molecular orbital energies (EHOMO and ELUMO), making them suitable for n-channel field-effect transistor (FET) applications. The benefits of introducing siloxane side chains to the DPPT core include enhanced solubility, low crystallization barrier, enantiotropic phase behavior, and much improved FET performance. The DPPT-Si-INCN film displayed low-lying HOMO (-5.82 eV) and LUMO (-4.60 eV) energy levels and an optical band gap as low as 1.22 eV, all of which suggest that this derivative can be quite resistant toward aerial oxidation. Thin films of these derivatives were prepared by the solution-shear method. A comparison of the solution-sheared films indicated that the molecular packing motif of DPPT-Si-INCN film was somehow different from that of DPPT-Si-DCV and DPPT-Si-RD, in which the π-π stacking tended to align orthogonally to the shearing direction. This specific π-π stacking alignment could have an impact on the electron mobility (µe) values in transistors based on the solution-sheared films.

Li-Ion Capacitor Integrated with Nano-network-Structured Ni/NiO/C Anode and Nitrogen-Doped Carbonized Metal-Organic Framework Cathode with High Power and Long Cyclability.

Lithium-ion capacitors (LICs) represent a new type of energy-storage devices, which have combined merits of high energy density Li-ion battery and high power density supercapacitor. Nevertheless, one significant challenge for LICs is the imbalanced kinetics between the fast capacitive cathode and relatively slow intercalation anode that limit the energy-storage performance. Here, the asymmetric LIC devices were developed based on a nitrogen-doped, carbonized zeolitic imidazolate framework (ZIF-8) cathode and a three-dimensional, nano-network-structured, conversion reaction-based Ni/NiO/C anode. These nanostructures associated with both the cathode and anode enable rapid electron and ions transport in the LIC devices, which allows the asymmetric LICs to be operated on either high energy mode (energy density of 114.7 Wh/kg at power density of 98.0 W/kg) or high power mode (power density of 60.1 kW/kg at energy density of 17.6 Wh/kg). The device also exhibited long-term cycle stability with 87% capacitance retention after 12 000 cycles. These results demonstrate that the rational design of nanoporous electrode structures can deliver a balanced, high-performance-activated cZIF-8|Ni/NiO/C-based lithium-ion capacitor.

Chemical mimicry of viral capsid self-assembly via corannulene-based pentatopic tectons.

Self-assembly of twelve pentatopic tectons, which have complementary edges or can be linked using either digonal or trigonal connectors, represents the optimal synthetic strategy to achieve spherical objects, such as chemical capsids. This process requires conditions that secure uninterrupted equilibria of binding and self-correction en route to the global energy minimum. Here we report the synthesis of a highly soluble, deca-heterosubstituted corannulene that bears five terpyridine ligands. Spontaneous self-assembly of twelve such tectons with 30 cadmium(II) cations produces a giant icosahedral capsid as a thermodynamically stable single product in high yield. Nuclear magnetic resonance (NMR) methods, mass spectrometry analyses, small-angle X-ray scattering, transmission electron microscopy, and atomic force microscopy indicate that this spherical capsid has an external diameter of nearly 6 nm and shell thickness of 1 nm, in agreement with molecular modeling. NMR and liquid chromatography evidences imply that chiral self-sorting complexation generates a racemic mixture of homochiral capsids.