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Development of bis(arylimino)acenaphthene (BIAN) copper complexes as visible light harvesters for photovoltaic and artificial photosynthetic applications

We demonstrate both experimentally and theoretically a new form of light storage based on Coherent Population Oscillations. It is shown to be phase preserving and robust to dephasing effects. © 2016 OSA.

2016 Conference on Lasers and Electro-Optics, CLEO 2016

Storage based on coherent population oscillations

Refluxing the dinuclear complex [Os2(CO)6(μ-OOCtBu)2] in acetonitrile affords the substituted derivative [Os2(CO)4(μ-OOCtBu)2(NCMe)2]. Their reaction with PPh3 in a 2:1 (Os:PPh3) ratio represents a convenient route to the 64-electron, tetraosmium chain [Os4(CO)8(μ-OOCtBu)4(PPh3)2]. © 2016 Elsevier B.V. All rights reserved.

Journal of Organometallic Chemistry

Convenient route to an electron-deficient Tetraosmium(I) Carboxylate chain

The phosphinoimino-2-imidazoline 4 was synthesized by a salt elimination reaction between LiNIPr [NIPr = 1,3-bis(2,6-(diisopropylphenyl)imidazolin-2-ylidenamino)] and 2-chloro-1,3,2-diazaphospholene. DFT study revealed that the HOMO of 4 involves the lone pair orbitals on the P atom and the N atom at the exocyclic P–N bond. Compound 4 displays selectivity in coordinating to acids. Thus, the N atom at the exocyclic P–N bond coordinates to a hard acid (HCl) which eventually led to the cleavage of the P–N bond, while the central P atom forms a dative bond with a soft Lewis acid, BH3. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Zeitschrift fur Anorganische und Allgemeine Chemie

Isolation of Phosphinoimino-2-imidazoline

All reported attempts to synthesize the tert-butyl-substituted adamantoid phosph(III)azane P4(NtBu)6have failed, leading to the classification of this molecule as inaccessible and a literature example of steric control in chemistry of phosphorus-nitrogen compounds. We now demonstrate that this structure is readily accessible by a solvent-free mechanochemical milling approach, highlighting the importance of mechanochemical reaction environments in evaluating chemical reactivity. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Fulltext

Angewandte Chemie - International Edition

The First Synthesis of the Sterically Encumbered Adamantoid Phosphazane P4(NtBu)6: Enabled by Mechanochemistry

Catalytic use of peroxomolybdate for asymmetric transformations has attracted increasing attention due to its catalytic properties and application in catalysis. Herein, we report chiral bisguanidinium dinuclear oxodiperoxomolybdosulfate [BG]2+ [(μ-SO4)Mo2O2 (μ-O2)2(O2)2]2- ion pair, as a catalyst for enantioselective sulfoxidation using aqueous H2O2 as the terminal oxidant. The ion pair catalyst is isolatable, stable and useful for the oxidation of a range of dialkyl sulfides. The practical utility was illustrated using a gram-scale synthesis of armodafinil, a commercial drug, with the catalyst generated in situ from 0.25 mol% of bisguanidinium and 2.5 mol% of Na2MoO4 ·2H2O. Structural characterization of this ion pair catalyst has been successfully achieved using single-crystal X-ray crystallography. © The Author(s) 2016.

Nature Communications

Bisguanidinium dinuclear oxodiperoxomolybdosulfate ion pair-catalyzed enantioselective sulfoxidation

In our attempt to prepare compound 4,5,9,10-tetraamino-2,7-bis(2-octyldodecyl)benzo[lmn] [3,8]phenanthroline-1,3,6,8(2H,7H)-tetraone (4NH2NDI) according to the reported procedure for constructing larger conjugated molecules, an unexpected by-product 2,8-bis(2-octyldodecyl)-5,5,11,11-tetraphenyl-5,6,11,12-tetrahydroimidazo[4′,5′:5,6]benzo[1,2,3,4-lmn]imidazo[4,5-f] [3,8]phenanthroline-1,3,7,9(2H,4H,8H,10H)-tetraone (4NHNDI) was obtained through the undesired hydrolysis of 4,5,9,10-tetrakis((diphenylmethylene)amino)-2,7-bis(2-octyldodecyl)benzo[lmn] [3,8]phenanthroline-1,3,6,8(2H,7H)-tetraone (4NNDI) when a drop of water was added in this reaction. The undesired hydrolysis was furthered confirmed by the direct hydrolysis of pure 4NNDI in organic solvent with a drop of aqueous HCl solution.4NHNDI was fully characterized by NMR and mass spectroscopy and was further confirmed through a single crystal analysis. The absorption and emission wavelengths of 4NHNDI were red-shifted ∼ 20 and 30 nm with the increased polar of the solvents due to the dipole-dipole interactions between 4NHNDI and the polarity solvents. Interestingly, 4NHNDI can act as an efficient anion sensor for fluoride ion over a wide range of other anions (ClO4-, Br-, BF4-, I-, NO3-, Cl-, PF6-, AcO-, HSO4- and CN-) owing to the four N-H fragments in the main backbone. Surprisingly, 4NHNDI didn't show any sensing behavior in aqueous solutions to all eleven anions including F- anion, which might be due to the steric effects from long alkyl chains in aqueous solution. However, this phenomenon could allow us to recover the quenched spectrum induced by F- anion through adding H2O in pure THF solution. © 2016 Published by Elsevier Ltd.

Dyes and Pigments

Synthesis, physical properties, and sensing behaviour of a novel naphthalenediimide derivative

Metal-free regioselective carboboration of arylnitriles with L2PhB: (1: L=oxazol-2-ylidene) catalyzed by Et3B afforded the unprecedented acyclic 2-aza-4-borabutadienes 2, thus demonstrating a new strategy to construct a B,C,N-mixed π-system involving B=C and C=N bonds. Thermal isomerization of 2 gave C-borylimines (3), and diverse reactivity of 2 a towards several substrates, such as H+, F+, O2, S, Se, and isonitriles, allowed construction of boron-containing heterocycles with various ring sizes, thus illustrating the utility of 2 as a synthetic building block. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Azaborabutadienes: Synthesis by Metal-Free Carboboration of Nitriles and Utility as Building Blocks for B,N-Heterocycles

Halogenation of the cluster Os3(CO)10(μ-SbPh2)2, 2, with PhICl2 or I2 affords the five-membered metallacyclic rings Os3(Cl)2(CO)10(μ-SbPh2)2, 3d and Os3(I)2(CO)10(μ-SbPh2)2, 3d-I, respectively, via oxidative addition across an Os-Os bond. The reaction of 2 with SbPh2Cl or SbPh2H gives the 3,5-fused rings Os3(X)(CO)9(μ-SbPh2)3, (X = Cl, 4a; H, 4b), respectively. Halogenation of 4 with PhICl2 gives the five-membered metallacyclic rings Os3(Cl)(X)(CO)9(SbPh2Cl)(μ-SbPh2)2 (X = Cl, 5a; H, 5b) via oxidative addition across an Os-Sb bond. The analogous reaction with I2 also results in oxidative addition across an Os-Sb bond, but this is followed by displacement of SbPh2I to afford a five-membered metallacycle containing a μ-I ligand, viz., Os3(μ-I)(X)(CO)9(μ-SbPh2)2 (X = Cl, 7a, H, 7b). © 2016 Elsevier B.V. All rights reserved.

Oxidative addition of halogen across an Os-Os or Os-Sb bond: Formation of five-membered osmium-antimony carbonyl rings

The reaction of carboxylic acids RCOOH (R = tBu, Ph, Fc) with [Ru3(CO)12] in refluxing acetonitrile afforded dark purple/red solids. These reacted with phosphines in a 2:1 (Ru:P) ratio to form phosphine-substitued derivatives of the electron-deficient tetraruthenium chains, viz., [Ru4(CO)8(μ-OOCR)4(PR′3)2] (where R′ = Ph or OMe). © 2015 Elsevier B.V.