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Visible light irradiation of CpIr(CO)2 (1) in pentafluorobenzontrile resulted in the formation of the two isomeric diiridium(II) complexes [CpIr(μ-CO)(C6F4CN)] 2 (3) and [CpIr(CO)(C6F4CN)]2 (4), while the analogous reaction of 1 in hexafluorobenzene to give [CpIr(μ-CO)(C6F5)]2 (3a) required UV irradiation. Complex 4 isomerizes to 3 under visible light irradiation. A reaction pathway to 4 involving aromatic nucleophilic substitution has been proposed on the basis of experimental and computational data. The isomerization of 4 to 3 is believed to proceed via a radical species resulting from homolytic fission of the Ir-Ir bond. © 2013 American Chemical Society.

World University root node

Organometallics

Photochemical reaction of CpIr(CO)2 with C6F 5X (X = CN, F): Formation of diiridium(II) complexes

2012 International Conference on Fiber Optics and Photonics, PHOTONICS 2012

Ultranarrow coherent population oscillation resonance in a Λ-type system

A measure of quantum correlation defined from an information-theoretic perspective, namely, quantum discord, is applied to study the time-evolved nonequilibrium state of the infinite anisotropic quantum XY spin chain in a transverse time-dependent field. In particular, we probe whether the collapse and revival of nearest-neighbor entanglement of the state seen with a varying initial applied field strength, at a fixed evolution time, may be predicted from the behavior of the quantum correlation measure. For this quantum many-body system, realizable with currently available technology, we find that the revival of entanglement of the evolved state occurs if there is an increase in quantum discord in the vicinity of entanglement collapse. © 2012 Europhysics Letters Association.

Fulltext

Quantum discord surge heralds entanglement revival in an infinite spin chain

The [4 + 2] cycloadduct between the 1-methyl-2-keto-1,2-dihydrophosphinine pentacarbonyltungsten complex and dimethyl acetylenedicarboxylate can be used as a precursor for the methylphosphaketene tungsten complex under UV irradiation at room temperature. Under these conditions, the phosphaketene complex easily loses CO to give the methylphosphinidene complex. Highly reactive alcohols and primary alkylamines trap both the phosphaketene and the phosphinidene complexes. Less reactive phenol and bulky amines together with alkynes and conjugated dienes only trap the phosphinidene complex. © 2012 American Chemical Society.

Generation and reactivity of methylphosphaketene in the coordination sphere of tungsten

The reaction between methylenechlorophosphine-pentacarbonyltungsten and an isobenzofuran affords a [4 + 2] adduct whose oxygen bridge is broken by BBr 3, leading to a 2-phosphanaphthalene. ©2012 American Chemical Society.

Organic Letters

A new route to a 2-phosphanaphthalene

A novel pyrene covalently-attached polyoxometalate (POM) hybrid has been synthesized and fully characterized. The attractive electronic and photophysical properties of pyrene derivatives make the hybrid promising for studying and understanding electron transfer mechanisms in organic-functionalized POMs. The hybrid has an electronic absorption at 450 nm, indicating that there is a strong electronic interaction between the organic pyreneimido group and inorganic hexamolybdate cluster. The electron transfer mechanism of the as-prepared hybrid is illuminated via the combined studies of theoretical calculations and transient absorption spectroscopy. Time-dependent density functional theory studies revealed that the strong electronic absorption at the visible region mainly comes from the optically allowed pi-pi{*} transitions of the pyreneimido component (S-0 to S-2 transition). The electron transfer process from the excited pyreneimido moiety to the inorganic POM cluster is at the time scale of similar to 700 fs, which could be ascribed to the internal conversion of singlet excited states from S-2 state to S-1 state. This study provided a clear understanding of the mechanism governing the electron transfer process in organoimido derivatives of POMs. This result might offer a new route for the design of new charge transfer hybrid clusters of organic functionalized POMs and crucial guidance for their applications in optical and electrical devices.

DALTON TRANSACTIONS

Experimental and theoretical studies on pyrene-grafted polyoxometalate hybrid

We investigate the decay time of a cavity containing strong dispersion achieved through electromagnetically induced transparency (EIT) in 4He*. We show that this concept is no longer relevant in the case of strong negative dispersion. © 2012 OSA.

Decay time in a cavity in slow or negative light regime

We study eperimentally and numerically the dynamics of a semiconductor laser subject to FOFs from two separate external cavities. Our results show that the inclusion of second FOF introduces rich control over the laser frequency. © 2012 OSA.

Semiconductor laser dynamics with two filtered optical feedbacks

A 2-ethoxycarbonylphosphaferrocene was reduced to the corresponding 2-hydroxymethyl derivative, which was condensed with pyrrole in a 2:1 ratio in the presence of BF 3 to give a phosphaferrocene-pyrrole- phosphaferrocene pincer ligand. This tridentate ligand, in turn, reacted with [Rh(acac)(CO) 2] to yield a rhodium carbonyl pincer complex. This complex was characterized by X-ray crystal structure analysis and tested in the hydroformylation of internal olefins. © 2012 American Chemical Society.

A new type of phosphaferrocene-Pyrrole-phosphaferrocene P-N-P pincer ligand

The first chiral phosphine-catalyzed activation of acrylates for intramolecular formal [2 + 4] reactions with unsaturated imines is described. The catalytic reactions afford N-heterocycles with exceptionally high diastereo- and enantioselectivities. The [2 + 4] products are amenable for further transformations to useful molecules such as chiral piperidines and multicyclic structures. © 2012 American Chemical Society.