HACS: Helical Auxetic Yarn Capacitive Strain Sensors with Sensitivity Beyond the Theoretical Limit.

The development of flexible strain sensors over the past decade has focused on accessing high strain percentages and high sensitivity (i.e., gauge factors). Strain sensors that employ capacitance as the electrical signal to correlate to strain are typically restricted in sensitivity because of the Poisson effect. By employing auxetic structures, the limits of sensitivity for capacitive sensors have been exceeded, which has improved the competitiveness of this modality of sensing. In this work, the first employment of helical auxetic yarns as capacitive sensors is presented. It is found that the response of the helical auxetic yarn capacitive sensors (termed as HACS) is dependent on the two main fabrication variables-the ratio of diameters and the helical wrapping length. Depending on these variables, sensors that respond to strain with increasing or decreasing capacitance values can be obtained. A greater auxetic character results in larger sensitivities accessible at smaller strains-a characteristic that is not commonly found when accessing high gauge factors. In addition, the highest sensitivity for auxetic capacitive sensors reported thus far is obtained. A mechanism of sensor response that explains both the variable capacitance response and the high gauge factors obtained experimentally is proposed.

Hydrogels as Soft Ionic Conductors in Flexible and Wearable Triboelectric Nanogenerators.

Flexible triboelectric nanogenerators (TENGs) have attracted increasing interest since their advent in 2012. In comparison with other flexible electrodes, hydrogels possess transparency, stretchability, biocompatibility, and tunable ionic conductivity, which together provide great potential as current collectors in TENGs for wearable applications. The development of hydrogel-based TENGs (H-TENGs) is currently a burgeoning field but research efforts have lagged behind those of other common flexible TENGs. In order to spur research and development of this important area, a comprehensive review that summarizes recent advances and challenges of H-TENGs will be very useful to researchers and engineers in this emerging field. Herein, the advantages and types of hydrogels as soft ionic conductors in TENGs are presented, followed by detailed descriptions of the advanced functions, enhanced output performance, as well as flexible and wearable applications of H-TENGs. Finally, the challenges and prospects of H-TENGs are discussed.

Octopus-Type Crown-Bisphthalocyaninate Anchor for Bottom-Up Assembly of Supramolecular Bilayers with Expanded Redox-Switching Capability.

Achievement of information storage at molecular level remains a pressing task in miniaturization of computing technology. One of the promising approaches for its practical realization is development of nanoscale molecular switching materials including redox-active systems. The present work demonstrates a concept of expansion of a number of available redox-states of self-assembled monolayers through supramolecular approach. For this, the authors synthesized an octopus-like heteroleptic terbium(III) bisphthalocyaninate bearing one ligand with eight thioacetate-terminated "tentacles" (octopus-Pc) and a ligand with four crown-ether moieties (H2 [(15C5)4 Pc]). It is shown that octopus-Pc forms stable monolayers on gold, where its face-on orientation allows for subsequent binding of crown-phthalocyanine molecules via potassium ion bridges. This chemistry is utilized to form a heterogeneous bilayer, in which a single molecule thick adlayer brings an additional redox-state to the system, thus expanding the multistability of the system as a whole. All four redox states available to this system exhibit characteristic absorbance in visible range, allowing for the switching to be easily read out using optical density measurements. The proposed approach can be used in wide range of switchable materials-single-molecule magnets, conductive, and optical devices, etc.

Switchable Aromaticity of Phthalocyanine via Reversible Nucleophilic Aromatic Addition to an Electron-Deficient Phosphorus(V) Complex.

Reversible nucleophilic addition to a phthalocyanine core was observed for the first time for the electron-deficient cationic phosphorus(V) complex [PcP(OMe)2]+, whose reaction with KOH afforded a highly distorted nonaromatic adduct bearing an OH group at one of the α-pyrrolic carbon atoms. This adduct was characterized by single-crystal X-ray diffraction, ESI HRMS, and NMR, and UV-vis spectroscopy, together with quantum-chemical modeling. The acidic treatment of this adduct restored aromaticity and recovered the starting cationic complex. The reversible aromaticity breakage resulted in dramatic changes in the photophysical properties of the studied complex, which could pave the way to novel switchable Pc-based compounds and materials.

Spin Crossover in Nickel(II) Tetraphenylporphyrinate via Forced Axial Coordination at the Air/Water Interface.

Coordination-induced spin crossover (CISCO) in nickel(II) porphyrinates is an intriguing phenomenon that is interesting from both fundamental and practical standpoints. However, in most cases, realization of this effect requires extensive synthetic protocols or extreme concentrations of extra-ligands. Herein we show that CISCO effect can be prompted for the commonly available nickel(II) tetraphenylporphyrinate, NiTPP, upon deposition of this complex at the air/water interface together with a ruthenium(II) phthalocyaninate, CRPcRu(pyz)2, bearing two axial pyrazine ligands. The latter was used as a molecular guiderail to align Ni···Ru···Ni metal centers for pyrazine coordination upon lateral compression of the system, which helps bring the two macrocycles closer together and forces the formation of Ni-pyz bonds. The fact of Ni(II) porphyrinate switching from low- to high-spin state upon acquiring additional ligands can be conveniently observed in situ via reflection-absorption UV-vis spectroscopy. The reversible nature of this interaction allows for dissociation of Ni-pyz bonds, and thus, change of nickel cation spin state, upon expansion of the monolayer.

Supramolecular control of the structure and receptor properties of an amphiphilic hemicyanine chromoionophore monolayer at the air/water interface.

Designing sensors for toxic compounds such as mercury salts in aqueous solutions still remains one of the most pressing tasks of modern chemical research, since many existing systems do not show enough sensitivity and/or response. In this regard, the opportunities offered by supramolecular approaches can be used to improve both these characteristics by creating a new self-organized smart system. Herein, we show that barium cations, that according to the data of X-ray standing waves do not bind directly to the ionophore molecules in the monolayers at the air/water interface, could be used to efficiently preorganize such molecules to achieve supramolecular architecture. We demonstrate that such preorganization ensures both low analyte detection threshold and high fluorescent response. We reveal the interrelation of the monolayer structure and receptor characteristics of a sensory system and show that such cation-induced preorganization in Langmuir monolayers of a hemicyanine dithia-aza-crown-substituted chromoionophore inhibits the formation of non-fluorescent aggregates with low receptor function, and allows the quantitative detection of mercury cations using a ratiometric fluorometric approach.

Long-Sought Redox Isomerization of the Europium(III/II) Complex Achieved by Molecular Reorientation at the Interface.

Redox isomerism, that is, the change of a metal cation valence state in organic complexes, can find promising applications in multistable molecular switches for various molecular electronic devices. However, despite a large number of studies devoted to such processes in organic complexes of multivalent lanthanides, redox-isomeric transformations were never observed for europium. In the present work, we demonstrate the unique case of redox isomerization of Eu(III)/Eu(II) complexes on the example of Eu double-decker octa-n-butoxyphthalocyaninate (Eu[(BuO)8Pc]2) under ambient conditions (air and room temperature). It is shown that assumption of the face-on orientation on the aqueous subphase surface, in which two of each phthalocyanine decks in Eu[(BuO)8Pc]2 are located in different media (air and water), leads to the intramolecular electron transfer that results in the formation of a divalent Eu(II) cation in the complex. Lateral compression of the thus-formed monolayer results in the reorientation of bisphthalocyaninate to the edge-on state, in which the ligands can be considered identical, and occurrence of the reverse redox-isomeric transformation into the complex with a trivalent Eu cation. Both redox-isomeric states were directly observed by X-ray absorption near-edge structure spectroscopy in ultrathin films formed under different conditions.

Fragmentation and slow autoneutralization of isolated negative molecular ions of phthalocyanine and tetraphenylporphyrin.

Macrocyclic tetrapyrrolic compounds, such as naturally occurring or artificial porphyrins and phthalocyanines, have unique and highly attractive properties for applications in medicine and technology. The interaction of free-base phthalocyanine (H2Pc) and tetraphenylporphyrin (H2TPP) molecules with low-energy (0-15 eV) electrons was studied in vacuo by means of negative ion resonant electron capture mass spectrometry. Close similarities in formation and decay of negative ions of these compounds were revealed. Efficient formation of long-lived molecular negative ions (MNIs) was observed in the incident electron energy range of 0-8 eV, unprecedentedly wide for organic compounds and comparable to the range characteristic to carbon atomic clusters, fullerenes. Experiments testify to the strong persistence of MNIs of both compounds to dissociative decay, isomerization, and electron autodetachment. Lifetimes of MNIs as a function of incident electron energy were measured and it was concluded that the isolated anions may retain additional electrons in a time scale of up to hundreds of seconds at standard temperature due to the high adiabatic electron affinity of these large molecules. For the representatives of dyes and photochromic compounds comprehensively studied in terms of interaction with light, the present work highlights yet another unique property of these molecules, namely the capability to attach and durably retain an additional electron of low, pre-ionization energy.