Mono-Heteroatom Substitution for Harnessing Excited-State Structural Planarization of Dihydrodibenzo[a,c]phenazines

With the aim of generalizing the structure–properties relationship of bending heterocyclic molecules that undergo prominent photoinduced structural planarization (PISP), a series of new dihydrodibenzo[ac]phenazine derivatives in which one nitrogen atom is replaced by oxygen ( PNO ), sulfur ( PNS ), selenium ( PNSe ), or dimethylmethanediyl ( PNC ) was strategically designed and synthesized. Compounds PNO , PNS , and PNSe have significantly nonplanar geometries in the ground state, which undergo PISP to give a planarlike conformer and hence a large emission Stokes shift. A combination of femtosecond early relaxation dynamics and computational approaches established an R*→I* (intermediate)→P* sequential kinetic pattern for PNS and PNSe , whereas PNO undergoes R*→P* one-step kinetics. The polarization ability of the substituted heteroatoms, which is in the order O<S<Se, correlates with their increase in π conjugation, and hence the Stokes shift of the emission is in the order PNO < PNS < PNSe . Compound PNSe with the largest PISP barrier was shown to be a highly sensitive viscosity probe. Further evidence for heteroatom-harnessing PISP is given by PNC , in which the dimethylmethanediyl substituent lacks lone pair electrons for π extension, showing the normal emission of the bent structure. The results led to the conclusion that PISP is ubiquitous in dihydrodibenzo[ac]phenazines, for which the driving force is elongation of the π delocalization to gain stabilization in the excited state.     

Polymer Template Synthesis of Flexible BaTiO3 Crystal Nanofibers

BaTiO₃ crystals are attractive materials due to their high dielectric properties, but they are brittle and inelastic ceramics, which limits their broader applications in emerging fields, such as flexible electronics. A scalable strategy for the fabrication of ultra‐flexible crystalline BaTiO₃ nanofiber (NF) films by a sol–gel electrospinning method, followed by a brief calcination, is reported. It facilitates the formation of perovskite BaTiO₃ crystals with intricate grain boundaries at a low temperatures by growing them within polymer NF templates. The ceramic films have a polymer‐like softness of 50 mN, a large Young's modulus of 61 MPa, and an elastic strain of 0.9%. Moreover, they have a low density of 28 mg cm^?3 and demonstrate superior softness without fracture after deformation. Piezoelectric sensors fabricated based on these films exhibit a high sensitivity of 80 ms with an output voltage of 1.05 V at a pressure of 100 kPa. This approach allows for the large‐scale fabrication of flexible BaTiO₃ crystal NF films.     

Design and Sensing Properties of a Self‐Assembled Supramolecular Oligomer

Supramolecular polymers are a class of macromolecules stabilized by weak non‐covalent interactions. These self‐assembled aggregates typically undergo stimuli‐induced reversible assembly and disassembly. They thus hold great promise as so‐called functional materials. In this work, we present the design, synthesis, and responsive behavior of a short supramolecular oligomeric system based on two hetero‐complementary subunits. These “monomers” consist of a tetrathiafulvalene‐functionalized calix[4]pyrrole (TTF‐C[4]P) and a glycol diester‐linked bis‐2,5,7‐trinitrodicyanomethylenefluorene‐4‐carboxylate (TNDCF), respectively. We show that when mixed in organic solvents, such as CHCl₃, CH₂ClCH₂Cl, and methylcyclohexane, supramolecular aggregation takes place to produce short oligomers stabilized by hydrogen bonding and donor–acceptor charge‐transfer (CT) interactions. The self‐associated materials were characterized by ¹H NMR and UV/Vis/NIR absorption spectroscopy, as well as by concentration‐ and temperature‐dependent absorption spectroscopy and dynamic light scattering (DLS) analyses of both the monomeric and oligomerized species. The self‐associated system produced from TTF‐C[4]P and TNDCF exhibits a concentration‐dependent aggregation behavior typical of supramolecular polymers. Further support for the proposed self‐assembly came from theoretical calculations. The fluorescence emitting properties of TNDCF are quenched under conditions that promote the formation of supramolecular aggregates containing TTF‐C[4]P and TNDCF. This quenching effect has been utilized as a probe for the detection of substrates in the form of anions (i.e., chloride) and nitroaromatic explosives (i.e., 1,3,5‐trinitrobenzene). Specifically, the addition of these substrates to mixtures of TTF‐C[4]P and TNDCF produced a fluorescence “turn‐on” response.     

Synthesis and selective recognition toward zinc ion of chiral poly(imine‐triazole)

A novel AB type of clickable monomer, (S)‐2‐[(2‐azido‐1‐phenylethylimino)methyl]‐5‐propargyloxyphenol (AMPP) was designed and polymerized to yield a class of main‐chain chiral poly(imine‐triazole)s through the metal‐free click reaction. With the thermally induced polymerization, the desired polytriazoles can be easily prepared in high yields by a stepwise heating‐up process and have the number‐average molecular masses ranging from 5.1 × 10³ to 58.1 × 10³ (polydispersity indices = 1.38?1.68). The polymers were characterized by Fourier Transform Infrared spectroscopy (FTIR), ¹H Nuclear Magnetic Resonance (NMR), and gel permeation chromatography, and their optical properties were studied by fluorescence and circular dichroism (CD) spectroscopies. As a chemosensor, these polymers exhibited a selective “turn‐on” fluorescence enhancement response toward Zn²⁺ ion over other cations such as Na⁺, K⁺, Mg²⁺, Ca²⁺, Ag⁺, Pb²⁺, Cd²⁺, Hg²⁺, Mn²⁺, and Ni²⁺ in dimethyl sulfoxide. However, the Zn²⁺‐induced fluorescence signal was subject to serious interference by Al³⁺, Cu²⁺, Cr³⁺, and Fe³⁺ ions. Interestingly, the chiral polymer showed distinctive changes in the CD spectra on complexation with Zn²⁺, which allowed for the discrimination of this ion in the presence of other species tested including those interfering ions observed in the fluorescent detection. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 2248–2257     

Fabrication of Carbon Nanotube Thin Films for Flexible Transistors by Using a Cross-Linked Amine Polymer

Owing to their remarkable properties, single-walled carbon nanotube thin-film transistors (SWCNT-TFTs) are expected to be used in various flexible electronics applications. To fabricate SWCNT channel layers for TFTs, solution-based film formation on a self-assembled monolayer (SAM) covered with amino groups is commonly used. However, this method uses highly oxidized surfaces, which is not suitable for flexible polymeric substrates. In this work, a solution-based SWCNT film fabrication using methoxycarbonyl polyallylamine (Moc-PAA) is reported. The NH₂-terminated surface of the cross-linked Moc-PAA layer enables the formation of highly dense and uniform SWCNT networks on both rigid and flexible substrates. TFTs that use the fabricated SWCNT thin film exhibited excellent performance with small variations. The presented simple method to access SWCNT thin film accelerates the realization of flexible nanoelectronics.     

Electrochemical sensors for environmental gas analysis

The application of electrochemical sensors for measurement of concentration of pollutant gases in air in the part-per-billion (10⁹) range is reviewed. Performance-limiting factors, particularly the effects of extremes and of relatively rapid changes in ambient temperature and humidity, are noted. Variations in composition of the electrolyte in the meniscus at the electrode–gas interface and instability of the solid–liquid–gas contact line, causing important variations in current due to background electrode reactions, are deduced and suggested as the reason for the performance limitations. Suggestions are made for mitigation through instrument design.     

An Ion-Exchangeable MOF with Reversible Dehydration and Dynamic Structural Behavior (NH4)2[Zn2(O3PCH2CH2COO)2]⋅5 H2O (BIRM-1)

(NH₄)₂[Zn₂(O₃PCH₂CH₂COO)₂]⋅5 H₂O (BIRM-1) is a new metal phosphonate material, synthesized through a simple hydrothermal reaction between zinc nitrate and 3-phosphonopropionic acid, using urea and tetraethylammonium bromide as the reaction medium. In common with other metal–organic framework materials, BIRM-1 has a large three-dimensional porous structure providing potential access to a high internal surface area. Unlike most others, it has the advantage of containing ammonium cations within the pores and has the ability to undergo cation exchange. Additionally, BIRM-1 also exhibits a reversible dehydration behavior involving an amorphization-recrystallization cycle. The ability to undergo ion exchange and dynamic structural behavior are of interest in their own right, but also increase the range of potential applications for this material. Here the crystal structure of this new metal phosphonate and its ion exchange behavior with K⁺ as an exemplar are studied in detail, and its unusual structure-reviving property reported.     

Near-IR Luminescent YbIII Coordination Polymers Composed of Pyrene Derivatives for Thermostable Oxygen Sensors

Oxygen-sensitive and near-infrared (NIR) luminescent Yb^III coordination polymers incorporating ligands based on pyrene derivatives were synthesized: Yb^III–TBAPy and Yb^III–TIAPy (TBAPy: 1,3,6,8-tetrakis(p-benzoate)pyrene; TIAPy: 1,3,6,8-tetrakis(3,5-isophthalic acid)pyrene). The coordination structures of these materials have been characterized by means of electrospray ionization mass spectrometry, X-ray diffraction analysis, and thermogravimetric analysis. Moreover, the porous structure of Yb^III–TIAPy has been evaluated by measuring its N₂ adsorption isotherm. The NIR luminescence properties of Yb^III–TBAPy and Yb^III–TIAPy have been examined by acquiring emission spectra and determining emission lifetimes under air or argon and in vacuo. Yb^III–TIAPy exhibited high thermal stability (with a decomposition temperature of 400 °C), intense luminescence (with an emission quantum yield under argon of 6.6 %), and effective oxygen-sensing characteristics. These results suggest that NIR luminescent Yb^III coordination polymers prepared using pyrene derivatives could have applications in novel thermo-stable oxygen sensors.