Abstract A boron difluoride formazanate dye that exhibits near‐infrared photoluminescence and electrochemiluminescence was produced via a straightforward two‐step synthesis. Examination of its solid‐state structure suggested the N ‐aryl substituents have significant quinoidal character, which narrows S 1 –S 0 energy gap leads to unique optoelectronic properties observed. Cyclic voltammetry studies revealed two oxidation waves reduction were electrochemically reversible....

The redox properties of verdazyl radicals are presented using cyclic voltammetry techniques. These can be reversibly reduced as well oxidized. Electron-donating and -withdrawing substituents have significant effects on the oxidation reduction potentials cell potential (E(cell) = | E(ox) degrees - E(red) |) for these radicals; a correlation between electron spin distribution is developed.

Getting in shape: Stable pointed-oval-shaped micelles of uniform size and shape (see TEM image) were prepared by extending the crystallization-driven living self-assembly method to crystalline core-forming polyferrocenylsilane diblock copolymers with corona-forming coblocks poly(2-vinylpyridine) polyphosphazene. The subsequently used as precursors hierarchical micelle architectures. Detailed facts importance specialist readers are published "Supporting Information". Such documents...

Two metals are better than one: Main-chain heterometallic block copolymers composed of iron- and cobalt-rich blocks (see picture) were synthesized through consecutive photocontrolled ring-opening polymerization (ROP) sila[1]ferrocenophanes dicarba[2]cobaltocenophanes followed by oxidation the cobaltocene-containing block. The redox properties self-assembly resulting in solution also studied. Detailed facts importance to specialist readers published as ”Supporting Information”. Such documents...

The solution self-assembly of block copolymers with a π-conjugated, crystalline, core-forming represents facile strategy toward the preparation semiconducting nanowires potential for high-tech applications. In this study, two asymmetric based on regioregular poly(3-hexylthiophene) (P3HT) and poly(methyl methacrylate) (PMMA), namely P3HT40-b-PMMA520 (6a) P3HT40-b-PMMA1100 (6b) (block ratios = 1:13 1:27.5, respectively) were prepared via atom transfer radical polymerization (ATRP) from P3HT...

With the aim of accessing colloidally stable, fiberlike, π-conjugated nanostructures controlled length, we have studied solution self-assembly two asymmetric crystalline-coil, regioregular poly(3-hexylthiophene)-b-poly(2-vinylpyridine) (P3HT-b-P2VP) diblock copolymers, P3HT23-b-P2VP115 (block ratio=1:5) and P3HT44-b-P2VP115 ratio=ca. 1:3). The studies were performed under a variety solvent conditions that selective for P2VP block. block copolymers prepared by using Cu-catalyzed azide-alkyne...

Irradiation of silicon-bridged [1]ferrocenophane [Fe(eta-C(5)H(4))(2)SiMe(2)] (1) in the presence substitutionally labile Lewis bases such as 4,4'-dimethyl-2,2'-bipyridine (Me(2)bpy) initiates ring-opening polymerization and oligomerization via cleavage an iron-cyclopentadienyl bond. A distribution cyclic polyferrocenylsilane c-PFS (PFS = [Fe(eta-C(5)H(4))(2)SiMe(2)](n)) a series oligomers (2(2)-2(7)) were isolated by column chromatography fully characterized. Varying temperature...

The self-assembly of block copolymers in selective solvents represents a powerful approach to functional core–shell nanoparticles. Crystallization the core can play critical role directing toward desirable, nonspherical morphologies with low mean interfacial curvature. Moreover, epitaxial growth processes have been implicated recent advances that permit access monodisperse cylinders, cylindrical comicelles segmented cores and/or coronas, and complex hierarchical architectures. However, how...

The straightforward synthesis and detailed characterization of nine substituted triarylformazanate boron difluoride complexes is reported. effect electron-donating (p-anisole) electron-withdrawing (p-benzonitrile) substituents on optical electrochemical properties, relative to phenyl substituents, was studied at two different positions within the formazanate ligand framework. Each BF2 characterized by 1H, 13C, 11B, 19F NMR spectroscopy, cyclic voltammetry, infrared UV–vis absorption emission...

The effect of extended π conjugation on the spectroscopic and electrochemical properties boron difluoride (BF2) formazanate complexes was studied by systematic comparison phenyl- naphthyl-substituted derivatives. Each BF2 described characterized (1)H, (13)C, (11)B, (19)F NMR spectroscopy, cyclic voltammetry, infrared UV-vis absorption emission mass spectrometry. X-ray crystallography electronic structure calculations were used to rationalize trends observed, including direct 3-cyano-,...

Systematic studies of the electrochemiluminescence (ECL) a boron difluoride formazanate dye reveal three distinct, voltage-dependent mechanisms light emission.

Abstract Evaluation of three subclasses boron difluoride formazanate complexes bearing o ‐, m and p ‐anisole N ‐aryl substituents (Ar) as readily accessible alternatives to dipyrromethene (BODIPY) dyes for cell imaging applications is described. While the wavelengths maximum absorption ( λ max ) emission em observed each subclass complexes, which differed by their carbon‐bound (R), were similar, quantum yields 7 a – c (R=cyano) enhanced relative 8 (R=nitro) 9 (R=phenyl). Complexes also...

The straightforward synthesis of a series 3-cyanoformazanate boron difluoride dyes is reported. Phenyl, 4-methoxyphenyl and 4-cyanophenyl N-substituted derivatives were isolated characterized by single-crystal X-ray crystallography, cyclic voltammetry, UV/Vis spectroscopy. compounds demonstrated to possess tunable, substituent-dependent absorption, emission, electrochemical properties, which rationalized through electronic structure calculations.

Water-soluble, high-molecular-weight polycobaltocenium polyelectrolytes have been prepared by ring-opening polymerization (ROP) techniques. Anionic of a strained 19-electron dicarba[2]cobaltocenophane followed oxidation in the presence ammonium chloride resulted formation oligomers with up to nine repeat units. Thermal ROP nitrate nitrate, redox-active cobalt-containing polyelectrolyte.

Two benzene-bridged N,N'-bis(isopropyl)6-oxoverdazyl diradicals 7a (1,4-benzene-bridged) and 7b (1,3-benzene-bridged) were prepared studied by an array of physicochemical techniques aimed at elucidating the intramolecular electronic magnetic coupling between verdazyl chromophores. The very high stability these permits comprehensive investigations their properties for first time. UV-vis spectra suggest negligible direct conjugative overlap involving radical SOMOs, although significant...

Copper(I) complexes of a diketiminate featuring CF3 groups on the backbone and dimethylphenyl substituents (4) nitroformazan (5) were synthesized shown by spectroscopy, X-ray crystallography, cyclic voltammetry, theory to contain copper(I) sites electron-deficient relative those supported previously studied comprising alkyl or aryl substituents. Despite their electron-poor nature, oxygenation LCu(CH3CN) (L = 4 5) at room temperature yielded bis(hydroxo)dicopper(II) compounds −80 °C...

Formazans react with boron triacetate to produce boratatetrazines, which can be reduced yield borataverdazyl radical anions—the first containing verdazyl radicals.

A gallium-bridged polyferrocene was prepared via spontaneous ring-opening polymerization of a galla[1]ferrocenophane. This organometallic polymer is thermally robust and can be purified handled under ambient conditions, making it an ideal candidate for incorporation into based materials offering alternative to existing polyferrocenes. The tBu group pointing toward the backbone serves as very sensitive NMR probe stereochemistry.

The synthesis and characterization of six transition metal complexes 3-cyano- 3-nitroformazans are described. Three different formazans were reacted with nickel(II) to produce bidentate formazan ligands. Mononuclear NiL2 (L = deprotonated formazan) or binuclear hydroxo-bridged (LNi)2(mu-OH) 2 species produced depending on the steric bulk N-aromatic substituents. 1,5-Bis(2-methoxyphenyl)-3-cyanoformazan acts as a tetradentate monoanionic ligand in copper(II) complex, whereas analogous...

Cylindrical block copolymer micelles with a crystalline poly(ferrocenyldimethylsilane) (PFDMS) core and long corona-forming are known to elongate through an epitaxial growth mechanism on addition of further PFDMS unimers. We now report that the semicrystalline homopolymer PFDMS28 monodisperse short (ca. 200 nm), cylindrical seed copolymers results in formation aggregated structures by end-to-end coupling form micelle networks. The resulting aggregates were characterized dynamic light...

Poly(cobaltoceniumethylene), a water-soluble cationic metal-containing polyelectrolyte, adopts chiral structure when bound electrostatically to DNA.