New synthetic methods for heterocyclic 1,3,2-dithiazolyl (DTA) radicals have been developed, and trends in the molecular spin distributions electrochemical properties of a series DTA are reported. The crystal structures [1,2,5]thiadiazolo[3,4-f][1,3,2]benzodithiazol-2-yl (TBDTA) [1,3,2]pyrazinodithiazol-2-yl (PDTA) determined. structure TBDTA (at 293 95 K) contains two molecules asymmetric unit, each which generates π-stacked arrays, one consisting antiparallel chains centrosymmetrically...

Stille coupling of 2- and 3-(tributylstannyl)thiophene derivatives with tetrabromobenzene followed by oxidative cyclization provides a simple, two-step synthetic route to two isomeric tetrathienoanthracene structures (13 14). The materials are characterized remarkable thermal stability, both in air (Tdec ≈ 400 °C) under nitrogen (sublimed no decomposition at 450–500 °C). Optical studies the parent alkylated compounds showed sky-blue photoluminescence quantum yields ranging between 0.17 0.40...

We report the synthesis and first electronic characterization of an atomically thin two dimensional π-conjugated polymer. Polymerization via Ullmann coupling a tetrabrominated tetrathienoanthracene on Ag(111) in ultra-high vacuum (UHV) produces porous 2D polymer network that has been characterized by scanning tunnelling microscopy (STM). High-resolution X-ray photoelectron spectroscopy (HRXPS) shows reaction proceeds distinct steps: dehalogenation brominated precursor, which begins at room...

We report the formation of highly-ordered self-assembled monolayers an achiral organic semiconductor molecule. STM results show spontaneous very large single domains ordered chiral monolayers. DFT calculations support identification halogen bonds as primary interactions that steer molecular self-assembly, leading to organizational chirality.

The evergrowing demand for cleaner, high-performing energetic materials (EMs) has led to a quest replacement of currently used toxic metal-based traditional compounds such as lead azide and styphnate.

The molecular radical 1,3,2-dithiazolo[4,5-b]pyrazin-2-yl (PDTA) exhibits magnetic bistability just above room temperature, undergoing a well-defined hysteretic phase change with TC↓ = 297(1) K and TC↑ 343(1) K. crystal structures of the two phases PDTA have been determined by single-crystal X-ray diffraction at 323(2) LT-PDTA consists diamagnetic (S 0) nearly superimposed π-dimer stacks, while that HT-PDTA comprises slipped stacks π-radicals 1/2). structural interconversion is suggested to...

Alkylation of the zwitterionic heterocycle 8-chloro-bis[1,2,3]dithiazolo[4,5-b:5',4'-e]pyridine (ClBP) with alkyl triflates affords 8-chloro-4-alkyl-4H-bis[1,2,3]dithiazolo[4,5-b:5',4'-e]pyridin-2-ium [ClBPR][OTf] (R = Me, Et, Pr). Reduction these salts decamethylferrocene corresponding ClBPR radicals as thermally stable crystalline solids. The have been characterized in solution by cyclic voltammetry and EPR spectroscopy. Measured electrochemical cell potentials computed (B3LYP/6-31G)...

A pair of isostructural bis-selenathiazolyl and bis-diselenazolyl radical conductors display weak (spin-canted) ferromagnetism with Tc values 18 K 27 respectively.

Three novel 1D, 2D and 3D coordination polymers were successfully isolated using nitrogen based 3,6-bis(2'-pyrimidyl)-1,2,4,5-tetrazine (BPymTz) 2,4,6-tris(2-pyrimidyl)-1,3,5-triazine (TPymT) ligands with Ag(I) ions. The formation of these supramolecular assemblies was templated through anion-π-system interactions.

The imaging and characterization of single-molecule reaction events is essential to both extending our basic understanding chemistry applying this challenges at the frontiers technology, for example, in nanoelectronics. Specifically, behavior individual molecules can elucidate processes critical controlled synthesis materials applications multiple nanoscale technologies. Here, we report an important semiconducting organic molecule through unprecedented observed with submolecular resolution...

An efficient and versatile synthetic route to resonance stabilized bisselenathiazolyl bisdiselenazolyl radicals 3 4 is described. Structural analysis of confirm that lattice π-delocalization energies are sufficient offset solid-state dimerization the two selenium-containing isostructural with all-sulfur based system 1. Variable temperature conductivity measurements indicate sequential replacement sulfur by selenium leads a progressive increase in reduction thermal activation energy.

Metal and metalloid phthalocyanines are an abundant established class of materials widely used in the dye pigment industry as well commercial photoreceptors. Silicon (SiPcs) among highest-performing n-type semiconductor this family when organic thin-film transistors (OTFTs) their performance solid-state arrangement often increased through axial substitution. Herein, we study eight axially substituted SiPcs integration into solution-processed OTFTs. Electrical characterization OTFTs, combined...

Main-group phthalocyanines are an emerging class of organic semiconductors with versatile charge carriers in field-effect transistors. In this review, overview is provided on the synthesis these building blocks and device performances.

Amidine-based ligand frameworks were employed to isolate a series of mononuclear lanthanide complexes. The N-2-pyridylimidoyl-2-pyridylamidine (Py2ImAm) undergoes metal-assisted hydrolysis yielding the 2-amidinopyridine (PyAm), which coordinates ions affording [Ln(acac)3(PyAm)], where Ln = Eu(III) (1), Gd(III) (2), Tb(III) (3), Dy(III) (4) along with Y(III) analogue (5). Eu(III), Tb(III), and congeners exhibit characteristic emissions red, green, yellow light, respectively, emission quantum...

The use of ternary additives in organic photovoltaics is a promising route for improving overall device performance. Silicon phthalocyanines (SiPcs) are ideal candidates due to their absorption profile, low cost, and ease synthesis chemical tunability. However, date, only few examples have been reported specific strategies aiding the design improved not established. In this study, we report relationship between additive solubility performance, demonstrating that performance maximized when...

Silicon phthalocyanines (R2–SiPcs) are an emerging class of high-performance n-type semiconductors used in organic electronics, which historically have suffered from operational instability air. We report the synthesis R2–SiPcs with varying degrees peripheral fluorination, R2–FxSiPcs (x = 0, 4, or 16), and different axial phenoxy groups leading to 12 derivatives 0 26 fluorine atoms molecular structure going non-operational devices ambient conditions fully air-stable operation thin-film...

Electronic waste is a growing challenge which needs to be addressed through the integration of high-performance sustainable materials. Green dielectric polymers such as poly(vinyl alcohol) (PVA) have favorable electrical properties but are challenging integrate into thin film electronics due their physical properties. For example, PVA suffers from poor formation and hygroscopic. Bilayer dielectrics with interfacial cross-linking can enable use surface chemistry by using hydrophobic...

2,4,6-Tris(2-pyrimidyl)-1,3,5-triazine has been synthesized using two approaches: <italic>via</italic> trimerization of 2-cyanopyrimidine at 160 °C and by the reaction with pyrimidine-2-carboximidamide.

Abstract Silicon phthalocyanines (R 2 ‐SiPcs) are a family of promising tunable materials for organic electronic applications. We report the chemistry synthesis axially substituted fluorinated SiPcs (tb‐Ph) ‐F x SiPc (where X = 0, 4, 8, or 16) and explore how degree fluorination effects optical properties. A new treatment with boron trichloride was included to obtain Cl from F SiPcs, activating axial position further functionalization. observed that as increased, so did electron affinity...

Abstract With the rise of internet things and applications such as smart packaging, need for low cost, disposable temperature sensors with minimum environmental impact are critical. In this study, we report fully printed capacitive made from bio-degradable dielectric materials. All layers were aerosol jet areal capacitance was characterized at several temperatures between room (22 ˚C) 80 °C. Using a bilayer structure, layer poly (vinyl alcohol) (PVA) encapsulated polycaprolactone (PCL)...

New synthetic routes to 1,2,3-dithiazolo-1,2,3-dithiazolylium salts, based on double Herz condensations of N-alkylated 2,6-diaminopyridinium salts with sulfur monochloride, have been developed. The two prototypal 1,2,3-dithiazolo-1,2,3-dithiazolyl radicals HBPMe and HBPEt prepared characterized in solution by cyclic voltammetry EPR spectroscopy. Measured electrochemical cell potentials computed (B3LYP/6-31G) gas-phase disproportionation enthalpies favor a low on-site Coulombic repulsion...

A synthetic sequence to salts of N-alkylated pyridine-bridged 1,2,3-thiaselenazolo-1,2,3-thiaselenazolylium cations [2]+ (R1 = Me, Et; R2 H) is described. The corresponding radicals 2 can be generated from the by chemical or electrochemical reduction. Crystals two are isostructural and consist interpenetrating pi-stacked arrays closed-shell Se-Se sigma-bonded dimers [2]2 laced together with numerous short intermolecular Se- - -Se, -S, -N contacts. Variable-temperature magnetic, conductivity,...

Reaction of N-alkylated pyridine-bridged bisdithiazolylium cations [1]+ (R1 =Me, Et; R2 =Ph) with selenium dioxide in acetic acid provides a one-step high-yield synthetic route to bisthiaselenazolylium [2]+ = Me, Ph). The corresponding radicals 1 and 2 can be prepared by chemical or electrochemical reduction the cations. Structural analysis has been achieved combination single-crystal powder X-ray diffraction methods. While two sulfur adopt different space groups (P3(1)21 for R1 Me P(-)1...

Probing optical and magnetic properties <italic>via</italic> subtle stereoelectronic effects in mononuclear Dy^III-complexes.

Axially substituted silicon phthalocyanines [(R3SiO)2-SiPc] have recently emerged as promising alternatives to fullerenes in organic photovoltaics (OPVs), with advances both molecular design and device fabrication resulting a fourfold improvement efficiency, bringing these materials closer commercial viability. Further refinements SiPc-based OPVs can only be achieved through exploration of their physical properties correlation performance metrics. In this work, we synthesized seven...