Phase Transformation, Exceptional Quenching Efficiency, and Discriminative Recognition of Nitroaromatic Analytes in Hydrophobic, Nonporous Zn(II) Coordination Frameworks.

Five-fold interpenetrated Zn(II) frameworks (1 and 2) have been prepared, and an irreversible phase transformation from 1 to 2 is found to occur through a dissolution-recrystallization process. Compound 1 exhibits the highest quenching efficiency (>96%) for nitrobenzene at 7 ppm among luminescent coordination polymers. Selective discrimination of nitroaromatic molecules including o-nitrophenol (o-NP), p-nitrophenol (p-NP), 2,4-dinitrophenol (DNP), and 2,4,6-trinitrophenol (TNP) is realized in 1 and 2 as a result of the fact that the framework-analyte interaction affords characteristic emission signals. This observation is the first case of a nonporous coordination framework for such discriminative detection. Notably, significant hydrophobicity is evident in the framework 1 because of its surface roughness, which accounts for the enhanced quenching ability.

Open-Shell and Closed-Shell Quinoid-Aromatic Conjugated Polymers: Unusual Spin Magnetic and High Charge Transport Properties.

While quinoidal moieties are considered as emerging platforms showing efficient charge transport and interesting open-shell diradical characteristics, whether these properties could be changed by extension to the conjugated polymer structure remains as a fundamental question. Here, we developed and characterized two conjugated polymers incorporating quinoids with different lengths, which have a stable close- and open-shell diradical character, respectively, namely, poly(quinoidal thiophene-thienylene vinylene) (PQuT-TV) and poly(quinoidal bithiophene-thienylene vinylene) (PQuBT-TV). A longer length of a quinoidal core led to enhanced diradical characteristics. Therefore, the longer core length of QuBT was favorable for the formation of an open-shell diradical structure in its monomer and in the quinoidal polymer. PQuBT-TV exhibited high spin characteristics observed by the strong ESR signal, a low band gap, and improved electrochemical stability. On the other hand, as QuT maintained a closed-shell quinoid structure, PQuT-TV exhibited high backbone coplanarity and strong intermolecular interaction, which was beneficial for charge transport and led to high hole mobility (up to 2.40 cm2 V-1 s-1) in organic field-effect transistors. This work successfully demonstrated how the control of the closed/open-shell character of quinoidal building blocks changes charge transport and spin properties of quinoidal conjugated polymers via quinoid-aromatic interconversion.

The Effect of Fluorine Substitution on the Molecular Interactions and Performance in Polymer Solar Cells.

Fluorine (F) substitution on conjugated polymers in polymer solar cells (PSCs) has a diverse effect on molecular properties and device performance. We present a series of three D-A type conjugated polymers (PBT, PFBT, and PDFBT) based on dithienothiophene and benzothiadiazole units with different numbers of F atoms to explain the influence of F substitution by comparing the molecular interactions of the polymers and the recombination kinetics in PSCs. The preaggregation behavior of PFBT and PDFBT in o-DCB at the UV-vis absorption spectra proves that both polymers have strong intermolecular interactions. Besides, more closely packed structures and change into face-on orientation of fluorinated polymers are observed in polymer:PC71BM blends by GIXD which is beneficial for charge transport and, ultimately, for current density in PSCs (4.3, 13.0, and 14.5 mA cm-2 for PBT, PFBT, and PDFBT, respectively). Also, the introduction of F atoms on conjugated backbones affects the recombination kinetics by suppressing bimolecular recombination, thereby improving the fill factor (0.41, 0.68, and 0.69 for PBT, PFBT, and PDFBT, respectively). Consequently, the PCE of PSCs reached 7.3% without any additional treatment (annealing, solvent additive, etc.) in the polymer containing difluorinated BT (PDFBT) that is much higher than nonfluorinated BT (PBT ∼ 1%) and monofluorinated BT (PFBT ∼ 6%).

Stable charge storing in two-dimensional MoS2 nanoflake floating gates for multilevel organic flash memory.

In this study, we investigated chemically exfoliated two-dimensional (2-D) nanoflakes of molybdenum disulfide (MoS2) as charge-storing elements for use in organic multilevel memory devices (of the printed/flexible non-volatile type) based on organic field-effect transistors (OFETs) containing poly(3-hexylthiophene) (P3HT). The metallic MoS2 nanoflakes were exfoliated in 2-methoxyethanol by the lithium intercalation method and were deposited as nano-floating gates between polystyrene and poly(methyl methacrylate), used as bilayered gate dielectrics, by a simple spin-coating and low temperature (<150 °C) process. In the developed OFET memory devices, electrons could be trapped/detrapped in the MoS2 nano-floating gates by modulating the charge carrier density in the active channel through gate bias control. Optimal memory characteristics were achieved by controlling the thickness and concentration of few-layered MoS2 nanoflakes, and the best device showed reliable non-volatile memory properties: a sufficient memory window of ∼23 V, programming-reading-erasing cycling endurance of >10(2) times, and most importantly, quasi-permanent charge-storing characteristics, i.e., a very long retention time (longer than the technological requirement of commercial memory devices (>10 years)). In addition, we successfully developed multilevel memory cells (2 bits per cell) by controlling the gate bias magnitude.

Reversible structural transformation and selective gas adsorption in a unique aqua-bridged Mn(II) metal-organic framework.

An aqua-bridged Mn metal-organic framework was prepared, and a dramatic structural transformation occurs upon solvent exchange-resolvation and desolvation-resolvation processes. The desolvated phase, formed by removing the aqua bridges, exhibits selective CO(2) uptake over N(2), H(2), and CH(4). Further, antiferromagnetic couplings are also found between Mn spins in the secondary building units.