HOMO Stabilisation in π‐Extended Dibenzotetrathiafulvalene Derivatives for Their Application in Organic Field‐Effect Transistors

Three new organic semiconductors, in which either two methoxy units are directly linked to a dibenzotetrathiafulvalene (DB‐TTF) central core and a 2,1,3‐chalcogendiazole is fused on the one side, or four methoxy groups are linked to the DB‐TTF, have been synthesised as active materials for organic field‐effect transistors (OFETs). Their electrochemical behaviour, electronic absorption and fluorescence emission as well as photoinduced intramolecular charge transfer were studied. The electron‐withdrawing 2,1,3‐chalcogendiazole unit significantly affects the electronic properties of these semiconductors, lowering both the HOMO and LUMO energy levels and hence increasing the stability of the semiconducting material. The solution‐processed single‐crystal transistors exhibit high performance with a hole mobility up to 0.04 cm² V^?1 s^?1 as well as good ambient stability.     

Unraveling the Crystal Structure of Lanthanide–Murexide Complexes: Use of an Ancient Complexometry Indicator as a Near‐Infrared‐Emitting Single‐Ion Magnet

Herein, we provide some structural evidence of the complexation color‐change of murexide solutions in presence of lanthanide, which has been used for decades in complexometric studies. For Ln=Sm to Lu and Y, the compounds crystallize as monomeric [Ln(Murex)₃] ? 11 H₂O with an N3O6 tricapped square‐antiprism environment, which are stable up to 250 °C. Single‐ion magnet (SIM) behavior is then observed on the Yb^III derivative in an original nine‐coordinated environment. In‐field slow relaxation (Δ=(15.6±1) K; τ₀=2.73×10^?6 s) is observed with a very narrow distribution of the relaxation time (α_max=0.09). Magnetic and photophysical properties can be correlated. On one hand the analysis of NIR emission spectrum permits to have access to crystal field parameters and to compare them with those extracted from dc measurements. On the other hand, magnetic measurements permit to identify the nature of the M _J states involved in the ²F_5/2→²F_7/2 luminescence spectrum. The gap between the low‐lying states is in agreement with the energy barrier obtained from magnetic slow‐relaxation measurement.     

Modulable and Highly Diastereoselective Carbometalations of Cyclopropenes

The copper‐catalyzed carbomagnesiation reaction of cyclopropenyl esters 1 leads to various substituted cyclopropanes species 3 in good yields with very high diastereoselectivities. The reaction proceeds through a syn‐chelated carbomagnesiation reaction and could be extended to various cyclopropenylmethyl ester derivatives 5 . The potential of this approach was illustrated by the preparation of two consecutive all‐carbon quaternary stereocenters. However, the carbometalation reaction needs to be performed at temperature ranging from ?35 to ?20 °C to avoid subsequent fragmentation reaction into stereodefined β,γ‐nonconjugated unsaturated esters 4 . Alternatively, the carbocupration reaction with organocopper species could also be performed to leads to configurationally stable cyclopropyl copper species 2[Cu] . Additionally, when the Lewis acid character of the copper center is decreased (i.e., RCuCNLi), the reaction proceed with an anti‐selectivity. The diastereodivergent behavior of these organometallic species is of synthetic interest, since both diastereomers syn‐ 3 and anti‐ 3 can be obtained, at will, from the same precursor cyclopropenyl esters 1 .     

Functionalization of a Ruthenium–Diacetylide Organometallic Complex as a Next‐Generation Push–Pull Chromophore

The design and preparation of an asymmetric ruthenium–diacetylide organometallic complex was successfully achieved to provide an original donor–π–[M]–π–acceptor architecture, in which [M] corresponds to the [Ru(dppe)₂] (dppe: bisdiphenylphosphinoethane) metal fragment. The charge‐transfer processes occurring upon photoexcitation of the push–pull metal–dialkynyl σ complex were investigated by combining experimental and theoretical data. The novel push–pull complex, appropriately end capped with an anchoring carboxylic acid function, was further adsorbed onto a semiconducting metal oxide porous thin film to serve as a photosensitizer in hybrid solar cells. The resulting photoactive material, when embedded in dye‐sensitized solar cell devices, showed a good spectral response with a broad incident photon‐to‐current conversion efficiency profile and a power conversion efficiency that reached 7.3 %. Thus, this material paves the way to a new generation of organometallic chromophores for photovoltaic applications.     

Metal‐Free Triplet Phosphors with High Emission Efficiency and High Tunability

Design of highly efficient phosphorescent emitters based on metal‐ and heavy atom‐free boron compounds has been demonstrated by taking advantage of the singlet fission process. The combination of a suitable molecular scaffold and appropriate electronic nature of the substituents has been utilized to tailor the phosphorescence emission properties in solution, neat solid, and in doped PMMA thin films.     

Estimation of band alignment at CdS/Cu2ZnSnS4 hetero-interface by direct XPS measurements

This paper aims to estimate the band alignment to CdS/CZTS hetero-interface by direct X-ray photoelectron spectroscopy (XPS) measurements. XPS was used to determinate the valence-band offset (VBO) directly by determining the valence band positions at the hetero-interface. The conduction band offset (CBO) value was estimated based on the band gap measurements by UV/Visible spectroscopy and VBO measurements. The position of valence band (VB) changes close to the CdS-CZTS interface and the CBO is cliff-like. The band alignment diagram indicates that the CdS-CZTS interface heterojunction is type II.     

Chiral N‐Heterocyclic Carbene Ligands Enable Asymmetric C−H Bond Functionalization

The asymmetric functionalization of C?H bond is a particularly valuable approach for the production of enantioenriched chiral organic compounds. Chiral N‐heterocyclic carbene (NHC) ligands have become ubiquitous in enantioselective transition‐metal catalysis. Conversely, the use of chiral NHC ligands in metal‐catalyzed asymmetric C?H bond functionalization is still at an early stage. This minireview highlights all the developments and the new advances in this rapidly evolving research area.     

A Molecular Strategy to Lock‐in the Conformation of a Perylene Bisimide‐Derived Supramolecular Polymer

Locking‐in the conformation of supramolecular assemblies provides a new avenue to regulate the (opto)electronic properties of robust nanoscale objects. In the present contribution, we show that the covalent tethering of a perylene bisimide (PBI)‐derived supramolecular polymer with a molecular locker enables the formation of a locked superstructure equipped with emergent structure–function relationships. Experiments that exploit variable‐temperature ground‐state electronic absorption spectroscopy unambiguously demonstrate that the excitonic coupling between nearest neighboring units in the tethered superstructure is preserved at a temperature (371 K) where the pristine, non‐covalent assembly exists exclusively in a molecularly dissolved state. A close examination of the solid‐state morphologies reveals that the locked superstructure engenders the formation of hierarchical 1D materials which are not achievable by unlocked assemblies. To complement these structural attributes, we further demonstrate that covalently tethering a supramolecular polymer built from PBI subunits enables the emergence of electronic properties not evidenced in non‐covalent assemblies. Using cyclic voltammetry experiments, the elucidation of the potentiometric properties of the locked superstructure reveals a 100‐mV stabilization of the conduction band energy when compared to that recorded for the non‐covalent assembly.     

Capturing the Monomeric (L)CuH in NHC‐Capped Cyclodextrin: Cavity‐Controlled Chemoselective Hydrosilylation of α,β‐Unsaturated Ketones

The encapsulation of copper inside a cyclodextrin capped with an N‐heterocyclic carbene (ICyD) allowed both to catch the elusive monomeric (L)CuH and a cavity‐controlled chemoselective copper‐catalyzed hydrosilylation of α,β‐unsaturated ketones. Remarkably, (α‐ICyD)CuCl promoted the 1,2‐addition exclusively, while (β‐ICyD)CuCl produced the fully reduced product. The chemoselectivity is controlled by the size of the cavity and weak interactions between the substrate and internal C?H bonds of the cyclodextrin.     

Rapid access to pyrido[1,2,5]triazepin-4-ones through intramolecular nucleophilic aromatic substitution

Several 3-substituted pyrido[1,2,5]triazepin-4-ones and their benzo counterparts have been prepared in three steps from commercial starting materials. The key step involves S_NAr-type intramolecular nucleophilic aromatic substitution of the appropriate hydrazone substrates.