Synthesis, photophysical properties, and computational studies of four-coordinate copper(I) complexes based on benzimidazolylidene N-heterocyclic carbene (NHC) ligands bearing aryl substituents
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The stacking of layers forming three-dimensional periodic structures is explored in the general case, where neither the layers nor the stacking need to be close-packed, and the connectivity number for the system may be either two or four. Procedures are described whereby all possible stacking variants can be systematically derived for a given number of layers, and for a given number of possible stacking positions. The latter depends on the structure of the layer and on the stacking vector.
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In this work, we present a detailed investigation of the low temperature emission properties of ZnSeO alloys by means of photoluminescence, micro-photoluminescence, and time-resolved photoluminescence. We show that the low temperature broad photoluminescence spectrum of ZnSeO attributed to the recombination of localized excitons is composed of sharp lines related to individual trapping states. Based on studies of photoluminescence thermal quenching from individual trapping states and photoluminescence dynamics, the mechanism of nonradiative recombination in ZnSeO alloys is discussed. Moreover, an unexpected decrease of the low temperature Stokes shift with increasing oxygen content is observed in contrast to what has been reported for GaAs based highly mismatched alloys. The possible origin of this effect is proposed.
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We examined the change in photoluminescence spectra of porous Si when it is oxidized then deoxidized chemically. After both steps, photoluminescence shifted to higher frequencies and increased in intensity. These shifts to higher frequencies indicate the photoluminescence is a result of the quantum size effect. Moreover, the increase in photoluminescence intensity after oxidation suggests that termination by hydrogen on the porous Si surface does not always play a key role in the photoluminescence mechanism.
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The synthesis of the first four-membered N-heterocyclic carbene is described. Depending on the substituents on the nitrogen atoms, it is possible to characterize at room temperature the carbene dimer or the free carbene. Crystallographic analyses are provided for these carbene species.
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Abstract The aromatic ring tethered vinylidenecyclopropane‐enes with less electron‐rich ortho‐substituents [e.g. (I)], isomerize to fused heterocycle [e.g. (II)] via a gold carbene intermediate generated from a rearrangement of vinylidenecyclopropane moiety.
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The golden state: Selective 5-exo- and 6-endo-cyclizations of an alkynyl benzothioamide have been achieved. The selectivity is controlled by the oxidation state of the gold precursor (+I or +III), yielding two new types of carbene ligand: an (aryl)(heteroaryl)carbene and a six-membered mesoionic carbene (see scheme). Mes=2,4,6-trimethylphenyl.
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The term “carbene” is applied to organic compounds described as CR2. A transition metal complex having this as a ligand is referred to as a “carbene complex”, and may be written MCR2 with a double bond between M and C. There is a large difference in stability and reactivity between complexes with and without heteroatoms (such as N, O, and S atoms) on the carbene carbon. They are thus frequently distinguished by referring to the former as Fischer carbene complexes and to the latter as Schrock carbene complexes, named for the chemists who first synthesized them. This chapter describes the features and reactivity of carbene complexes.
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Abstract Two‐electron reduction of carbene‐supported 9‐bromo‐9‐borafluorenes with excess KC 8 , Na, or Li‐naphthalenide affords six N‐heterocyclic carbene (NHC)‐ or cyclic(alkyl)(amino) carbene (CAAC)‐stabilized borafluorene anions ( 3 – 8 )‐the first isolated and structurally authenticated examples of the elusive 9‐carbene‐9‐borafluorene monoanion. The electronic structure, bonding, and aromaticity of the boracyclic anions were comprehensively investigated via computational studies. Compounds 5 and 8 react with metal halides via salt elimination to give new B‐E (E=Au, Se, Ge)‐containing materials ( 9 – 12 ). Upon reaction with diketones, the carbene ligand cleanly dissociates from 5 or 8 to yield new B‐O containing spirocycles ( 13 – 14 ) that cannot be easily obtained using “normal” valent borafluorene compounds. Collectively, these results support the notion that carbene‐stabilized monoanionic borafluorenes may serve as a new platform for the one‐step construction of higher‐value boracyclic materials.
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