Stable All-Organic Radicals with Ambipolar Charge Transport.

A series of neutral long-lived purely organic radicals based on the stable [4-(N-carbazolyl)-2,6-dichlorophenyl]bis(2,4,6-trichlorophenyl)methyl radical adduct (Cbz-TTM) is reported herein. All compounds exhibit ambipolar charge-transport properties under ambient conditions owing to their radical character. High electron and hole mobilities up to 10-2 and 10-3  cm2 V-1 s-1 , respectively, were achieved. Xerographic single-layered photoreceptors were fabricated from the radicals studied herein, exhibiting good xerographic photosensitivity across the visible spectrum.

Bis(triisopropylsilylethynyl)-substituted pyrene-fused tetraazaheptacene: synthesis and properties.

The synthesis and characterisation of a pyrene-fused tetraazaheptacene that is constituted of two terminal pyrene units and a central tetraazaanthracene core are reported. The optoelectronic properties (experimental and calculated) of this heptacene derivative are discussed together with its charge transport properties in thin films.

Hexaazatrinaphthylenes with different twists.

A synthetic strategy that allows the induction of twist angles of different sizes in 5,6,11,12,17,18-hexaazatrinaphthylene (HATNA) chromophores is reported. The different twist angles are accompanied by measurable changes in the emission and electrochemical characteristics of HATNA.

Advantages of preoperative localization and surgical resection of metastatic axillary lymph nodes using magnetic seeds after neoadjuvant chemotherapy in breast cancer.

PURPOSE: To assess the safety and effectiveness of magnetic seeds in preoperative localization and surgical dissection of metastatic axillary lymph nodes (LN+) in breast cancer patients with axillary involvement, after neoadjuvant chemotherapy (NAC). In addition, to assess the impact of targeted axillary dissection (TAD) in reducing the rate of false negatives (FN) in sentinel lymph node biopsy (SLNB). MATERIALS AND METHODS: A cross-sectional prospective cohort study was conducted from April 2017 to September 2019, including breast cancer patients with axillary lymph node involvement treated with NAC. Prior to NAC, the LN+ were marked by ultrasound-guided clip insertion. After NAC, a magnetic seed (Magseed®) was inserted in the clip-marked lymph node (MLN). During surgery, the MLN was located and removed with the aid of a magnetic detection probe (Sentimag®) and the sentinel lymph node was removed. Axillary lymph node dissection (ALND) was used to determine the rate of FN for SLNB alone and the combination of SLNB and MLN dissection, called TAD. RESULTS: The study included 29 patients (mean age, 55; range, 30-78 years). Selective preoperative localization and surgical dissection were successful for all 30 MLNs (100%). The MLN corresponded to the SLN in 50% of cases. After ALND, there were 21.4% (3/14) FN with SLNB alone and 5.9% (1/17) with TAD. CONCLUSIONS: Following NAC, selective surgical removal of MLN by preoperative localization using magnetic seeds is a safe and effective procedure with a success rate of 100%. Adding TAD reduces the rate of FN associated with SLNB alone.

Charge transport modulation in pseudorotaxane 1D stacks of acene and azaacene derivatives.

Acenes have received a lot of attention because of their inherent and tunable absorbing, emissive, and charge transport properties for electronic, photovoltaic, and singlet fission applications, among others. Such properties are directly governed by molecular packing, and therefore, controlling their arrangement in the solid state is of utmost importance in order to increase their performance. Herein, we describe a new solid-state ordering strategy that allows obtaining 1D mixed π-stacks of acene and azaacene derivatives. In addition, we illustrate that charge transport can be modulated by the electronic nature of the encapsulated phenazine, opening new perspectives in the design, preparation and development of supramolecular organic semiconductors.

A thiadiazole-capped nanoribbon with 18 linearly fused rings.

Polycyclic aromatic hydrocarbons that extend over 2 nm in one dimension are seen as monodisperse graphene nanoribbons, which have attracted significant attention for a broad range of applications in organic electronics and photonics. Herein we report the synthesis of a stable bisthiadiazole-capped pyrene-containing nanoribbon with 18 linearly fused rings (NR-18-TD). Thanks to the presence of alternating tert-butyl and tri-iso-butylsilyl groups, NR-18-TD is highly soluble in organic solvents and therefore its structure and fundamental optoelectronic, redox and electrical properties could be unambiguously established. This work illustrates that NR-18-TD is a promising soluble NR-based n-type semiconductor for applications in organic electronics.

Energy Level Alignment at Metal/Solution-Processed Organic Semiconductor Interfaces.

Energy barriers between the metal Fermi energy and the molecular levels of organic semiconductor devoted to charge transport play a fundamental role in the performance of organic electronic devices. Typically, techniques such as electron photoemission spectroscopy, Kelvin probe measurements, and in-device hot-electron spectroscopy have been applied to study these interfacial energy barriers. However, so far there has not been any direct method available for the determination of energy barriers at metal interfaces with n-type polymeric semiconductors. This study measures and compares metal/solution-processed electron-transporting polymer interface energy barriers by in-device hot-electron spectroscopy and ultraviolet photoemission spectroscopy. It not only demonstrates in-device hot-electron spectroscopy as a direct and reliable technique for these studies but also brings it closer to technological applications by working ex situ under ambient conditions. Moreover, this study determines that the contamination layer coming from air exposure does not play any significant role on the energy barrier alignment for charge transport. The theoretical model developed for this work confirms all the experimental observations.

K-Conjugated Dibenzoazahexacenes.

The synthesis and properties of two highly stable K-conjugated dibenzoazahexacenes are reported. Single-crystal X-ray, optoelectronic, and electrochemical characterization combined with theoretical studies show a favorable molecular packing and an optimal energy alignment of their frontier orbitals for charge transport. Electrical characterization illustrates that the preferential transport of holes or electrons depends on the number of N atoms in the aromatic framework.

Bisthiadiazole-Fused Tetraazapentacenequinone: An Air-Stable Solution-Processable n-Type Organic Semiconductor.

The synthesis and characterization of a tetraazapentacenequinone fused to two thiadiazoles is reported. This linear derivative constituting seven fused rings shows a very low LUMO level (-4.46 eV) and a low HOMO-LUMO gap (1.77 eV). Its high solubility, endowed by four triisopropylsilyl groups, allows the fabrication of air-stable field-effect transistors by liquid deposition methods that show electron mobilities up to 2.42 × 10(-3) cm(2) V(-1) s(-1) without any device optimization.

An electron-conducting pyrene-fused phenazinothiadiazole.

A pyrene-fused phenazinothiadiazole that shows electron mobilities (µe = 0.016 cm(2) V(-1) s(-1)) two orders of magnitude higher than those reported for pyrene-fused pyrazaacenes is described.