Cleavage of an Aromatic C-C Bond in Ferrocene by Insertion of an Iridium Nitrido Nitrogen Atom.

The intermolecular cleavage of C-C bonds is a rare event. Herein, we report on a late transition-metal terminal nitrido complex, which upon oxidation undergoes insertion of the nitrido nitrogen atom into the aromatic C-C bond of ferrocene. This reaction path was confirmed through 15N and deuterium isotope labeling experiments of the nitrido complex and ferrocenium, respectively. Cyclic voltammetry and UV/vis spectroscopy monitoring of the reaction revealed that oxidation is the initial step, yielding the tentative radical cationic nitrido complex, which is experimentally supported by extended X and Q-band electron paramagnetic resonance (EPR) and ENDOR, UV/vis, vT 1H NMR, and vibrational spectroscopic data. Density functional theory (DFT) and multireference calculations of this highly reactive intermediate revealed an S = 1/2 ground state. The high reactivity can be traced to the increased electrophilicity in the oxidized complex. Based on high-level PNO-UCCSD(T) calculations and UV/vis kinetic measurements, it is proposed that the reaction proceeds by initial electrophilic exo attack of the nitrido nitrogen atom at the cyclopentadienyl ring and consecutive ring expansion to a pyridine ring.

Dinuclear tethered pyridine, diimine complexes.

The regioselective borylation of pyridine precursors, followed by Suzuki coupling with dihalogenated linker molecules, provides access to tethered ligands. Complexation with MX2 salts results in the formation of dinuclear metal compounds. Syntheses and crystal structures are reported along with a discussion on the rigidity/flexibility of these new ligand systems.

Boryl- and Silyl-Substituted Mixed Sandwich Compounds of Scandium.

An improved, one-pot synthesis of the linear sandwich compound [Sc(η5 -C5 H5 )(η8 -C8 H8 )] is presented. The synthetic procedure is amenable to boryl- and silyl-substituted cyclopentadienyl and cyclooctatetraenyl ligands, thereby yielding the first functionalized derivatives. We found that the synthesis of the silyl-substituted mixed sandwich complexes produces higher yields when the ligand exchange is carried out stepwise, by isolating the intermediate trimethylsilylated half-sandwich complex [Sc(η8 -C8 H7 SiMe3 )Cl(THF)] (THF=tetrahydrofuran). The molecular structures of the parent complex, as well as of its mono-boryl-substituted derivatives, have been determined by single-crystal X-ray diffraction. In addition, the optical and electrochemical properties of the mixed sandwich complexes are reported.

Synthesis, Structures, and Photophysical Properties of a Series of Rare Near-IR Emitting Copper(I) Complexes.

Herein, we report on the synthesis and structural characterization of a series of trigonal and tetrahedral cationic copper(I) complexes, bearing phosphine or N-heterocyclic carbene ligands as donors, with benzthiazol-2-pyridine (pybt) and benzthiazol-2-quinoline (qybt) acting as π-chromophores. The compounds are highly colored due to their 1MLCT (MLCT = metal-to-ligand charge transfer) states absorbing between ca. λabs = 400-500 nm, with 1ILCT (ILCT = intraligand charge transfer) states in the UV region. The relative shifts of the S0→S1 absorption correlate with the computed highest occupied molecular orbital-lowest unoccupied molecular orbital gaps, the qybt complexes generally being lower in energy than the pybt ones due to the larger conjugation of the quinoline-based ligand. The compounds exhibit, for CuI complexes, rare intense long-lived near-IR emission with λmax ranging from 593 to 757 nm, quantum yields of up to Φ = 0.11, and lifetimes τ of several microseconds in the solid state as well as in poly(methyl methacrylate) films. Although a bathochromic shift of the emission is observed with λmax ranging from 639 to 812 nm and the lifetimes are greatly increased at 77 K, no clear indication for thermally activated delayed fluorescence was found, leaving us to assign the emission to originate from a 3(Cu→pybt/qybt)MLCT state. The red to near-IR emission is a result of incorporation of the sulfur into the chromophore ligand, as related nitrogen analogues emit in the green to orange region of the electromagnetic spectrum. The photophysical results and conclusions have further been corroborated with density functional theory (DFT)/time-dependent DFT calculations, confirming the nature of the excited states and also the trends of the redox potentials.

TiO2 nanotubes in dye-sensitized solar cells: critical factors for the conversion efficiency.

Particle vs tube: The present paper systematically investigates a range of fundamental geometrical and structural features of TiO(2) nanotube layers and their effect on the dye-sensitized solar cell conversion efficiency, to deduce the most promising strategies for improvement. It is found that the performance of the cells strongly depends on the morphology and crystalline structure of the nanotubes.