Synthesis and Photophysical Studies of Copper(I) CAAC Half-Sandwich Complexes as a Highly Modifiable Class of Emitters.

Cyclopentadienyls are well-known strong donor ligands and have been successfully employed in catalysis as they tolerate a variety of substituents to adjust their steric and electronic properties. Although such highly modifiable ligands are of great interest for luminescence and photocatalytic applications, studies of Cp-containing photoactive transition-metal complexes are quite rare. In this work, we present a structural, electrochemical, and first elaborated photophysical investigation of a series of copper(I) half-sandwich complexes bearing cyclic alkyl(amino)carbenes (CAACs) as chromophore ligands and compare them with [Cu(Cp)(IDipp)] and [Cu(Cp*)(IDipp)] bearing a traditional -heterocyclic carbene.

Trigonal Copper(I) Complexes with Cyclic (Alkyl)(amino)carbene Ligands for Single-Photon Near-IR Triplet Emission.

Molecular near-IR (NIR) triplet-state emitters are of importance for the development of new, organic-electronics-based telecommunication technologies as optical fibers operating in the corresponding spectral bands allow for data transfer over much longer distances due to the significantly lower attenuation. However, achieving such low-energy triplet excited states with good radiative rate constants is very challenging, and studies regarding the single-photon emission of organometallics in this energy range are scarce. We have prepared a series of trigonal Cu CAAC complexes bearing chelating ligands with O, N, S, and Se donor atoms and studied their photophysical properties in this context.

Aggregation-Induced Dual Phosphorescence from (o-Bromophenyl)-Bis(2,6-Dimethylphenyl)Borane at Room Temperature.

Designing highly efficient purely organic phosphors at room temperature remains a challenge because of fast non-radiative processes and slow intersystem crossing (ISC) rates. The majority of them emit only single component phosphorescence. Herein, we have prepared 3 isomers (o, m, p-bromophenyl)-bis(2,6-dimethylphenyl)boranes.

Cyclic (Amino)(aryl)carbenes Enter the Field of Chromophore Ligands: Expanded π System Leads to Unusually Deep Red Emitting Cu Compounds.

A series of copper(I) complexes bearing a cyclic (amino)(aryl)carbene (CAArC) ligand with various complex geometries have been investigated in great detail with regard to their structural, electronic, and photophysical properties. Comparison of [CuX(CAArC)] (X = Br (), Cbz (), acac (), Phacac (), Cp (), and Cp* ()) with known Cu complexes bearing cyclic (amino)(alkyl), monoamido, or diamido carbenes (CAAC, MAC, or DAC, respectively) as chromophore ligands reveals that the expanded π-system of the CAArC leads to relatively low energy absorption maxima between 350 and 550 nm in THF with high absorption coefficients of 5-15 × 10 M cm for -. Furthermore, - show intense deep red to near-IR emission involving their triplet excited states in the solid state and in PMMA films with λ = 621-784 nm.

Palladium-Catalyzed Homocoupling of Highly Fluorinated Arylboronates: Studies of the Influence of Strongly vs Weakly Coordinating Solvents on the Reductive Elimination Process.

C-C reductive elimination from [PdL(CF)] to form polyfluorinated biaryls has been a challenge for over 50 years. Thus, palladium-catalyzed homocoupling of arylboronates (Ar-Bpin) containing two -fluorine substituents is very difficult, as the reaction typically stops at the [PdL(Ar)] stage after two transmetalation steps. The transmetalated complexes [Pd(MeCN)(CF)] (), [Pd(MeCN)(2,4,6-CFH)] (), and -[Pd(MeCN)(2,6-CFH)] () have been isolated from the reaction of Ar-Bpin with Pd(OAc) in acetonitrile solvent, with no homocoupling observed.

Copper-Catalyzed Triboration of Terminal Alkynes Using B pin : Efficient Synthesis of 1,1,2-Triborylalkenes.

We report herein the catalytic triboration of terminal alkynes with B pin (bis(pinacolato)diboron) using readily available Cu(OAc) and P Bu . Various 1,1,2-triborylalkenes, a class of compounds that have been demonstrated to be potential matrix metalloproteinase (MMP-2) inhibitors, were obtained directly in moderate to good yields. The process features mild reaction conditions, a broad substrate scope, and good functional group tolerance.

Triarylborane-Based Helical Donor-Acceptor Compounds: Synthesis, Photophysical, and Electronic Properties.

The synthesis and characterization of 10-(dimesitylboryl)-N,N-di-p-tolylbenzo[c]phenanthren-4-amine (3-B(Mes) -[4]helix-9-N(p-Tol) 1) and 13-(dimesitylboryl)-N,N-di-p-tolyldibenzo[c,g]phenanthren-8-amine (3-B(Mes) -[5]helix-12-N(p-Tol) 2) are reported herein. Their electrochemical and photophysical properties have been studied experimentally and theoretically. The donor and acceptor-substituted helicene derivatives exhibit moderate fluorescence quantum yields in THF (Φ =0.