Photochemical reactivities of cyclic α-phenyl-β,γ-enones. Singlet 1,3-acyl shift, decarbonylation and unquenchable oxa-di-π-methane reactions upon direct irradiation

2010 ◽  
Vol 107 (9) ◽  
pp. 549-562 ◽  
Author(s):  
Margareth J. C. M. Koppes ◽  
Hans Cerfontain
Molecules ◽  
2019 ◽  
Vol 24 (8) ◽  
pp. 1502 ◽  
Author(s):  
Ming Rao ◽  
Wanhua Wu ◽  
Cheng Yang

Visible-light-driven photocatalytic supramolecular enantiodifferentiating dimerization of 2-anthracenecarboxylic acid (AC) through triplet-triplet annihilation (TTA), mediated by the Schiff base Pt(II) complex (Pt-1, Pt-2, and Pt-3) was studied. The host concentration and the temperature effects on the stereoselectivity were comprehensively investigated. Increasing the concentration of sensitizers/hosts significantly enhanced the conversion of the photoreaction but led to reduced enantioselectivities of the chiral photodimers 2 and 3 when the photoreaction was triggered by a 532 nm laser, which was in contrast with the results obtained by direct irradiation of AC with a 365 nm light-emitting diode (LED) lamp, due to the aggregation of the sensitizer/host in water. The cyclization of AC through triplet-triplet annihilation displayed significant temperature dependency when Pt-3 was employed as the sensitizer/host. Increasing the temperature from 0 °C to 30 °C with 5% equiv. of Pt-3 led to a great increase of the ee of 2 from 2.1% to 31.6%. However, hardly any temperature dependency was observed when the photodimerization was mediated by other sensitizers and/or hosts, or the photoreaction was triggered directly with a 365 nm LED lamp.


2020 ◽  
Vol 9 (3) ◽  
pp. 177-184
Author(s):  
Affi Nur Hidayah ◽  
◽  
Yuliati Herbani ◽  

In this work we investigated the optical and electrical properties of Au-Ag nanoalloys in various volume ratios. The nanoparticles have been prepared from gold and silver ions reduced by direct irradiation femtosecond laser. The samples were added into a quartz cuvette and irradiated for 10 minutes. Each sample was observed the optical property where surface plasmon resonance (SPR) peak was existed. In addition, electrical conductivity of the colloids was derived from the measurement of the correspond zeta potential by dynamic light scattering (DLS) method. The results showed that the SPR peak of Au-Ag nanoalloy were shifted almost linearly in between 409 nm for Ag and 530 nm for Au depending on their volume fraction. The conductivity measurement showed that Au0Ag100 (pure Ag) nanoparticles has the highest value and Au100Ag0 (pure Au) nanoparticles has the lowest value, and interestingly, Au-Ag nanoalloys have the values between Au0Ag100 and Au100Ag0. Briefly, this work revealed that both optical and electrical properties of Au-Ag nanoalloys can be easily tuned by regulating the volume fraction between the two elements.


1989 ◽  
Vol 67 (1) ◽  
pp. 82-87 ◽  
Author(s):  
Christopher Owen Bender ◽  
Douglas Dolman

The direct irradiation of 5-cyano-2,3-benzobicyclo[4.2.0]octa-2,4,7-triene (18) led to 6-cyanobenzocyclooctatetraene (17; Φ = 0.00075), 6-cyanobenzosemibullvalene (14; Φ = 0.0003), and 2-cyanonaphthalene (Φ = 0.00015). The triplet excited state of 18, generated by sensitization with a variety of ketone sensitizers (e.g., Michler's ketone and acetophenone), showed no unimolecular reactivity. Compound 18 does not participate in Zimmerman di-π-methane rearrangement; the potential product from such a transformation, 8-cyanobenzosemibullvalene (19), was, however, isolated from direct (Corex filter; Φ = 0,0010) irradiation of the semibullvalene 14. Deuterium labelling experiments suggest that 14 derives from a mechanism involving initial C4—C8 bonding of 18, and that cyclooctatetraene 17 is probably formed by simple electrocyclic opening of the cyclobutene ring of 18. Keywords: photochemistry, rearrangement mechanism, di-π-methane, semibullvalenes.


2021 ◽  
Author(s):  
Yasuhiro Kuramitsu ◽  
Takumi Minami ◽  
Takamasa Hihara ◽  
Kentaro Sakai ◽  
Takahiro Nishimoto ◽  
...  

Abstract Atomically thin graphene is a transparent, highly electrically and thermally conductive, light-weight, and the strongest material. To date, graphene has found applications in many aspects including transport, medicine, electronics, energy, defense, and desalination. We demonstrate another disruptive application of graphene in the field of laser-ion acceleration, in which the unique features of graphene play indispensable role. Laser driven ion sources have been widely investigated for pure science, plasma diagnostics, medical and engineering applications. Recent developments of laser technologies allow us to access radiation regime of laser ion acceleration with relatively thin targets. However, the thinner target is the less durable and can be easily broken by the pedestal or prepulse through impact and heating prior to the main laser arrival. One of the solutions to avoid this is plasma mirror, which is a surface plasma created by the foot of the laser pulse on an optically transparent material working as an effective mirror only for the main laser peak. So far diamond like carbon (DLC) is used to explore the ion acceleration in extremely thin target regime (< 10 nm) with plasma mirrors, and it is necessary to use plasma mirrors even in moderately thin target regime (10-100 nm) to realize energetic ion generation. However, firstly DLC is not 2D material, and therefore, it is very expensive to make it thin and flat. Moreover, graphene is stronger than diamond at extremely thin regime, and much more reasonable for mass-production. Furthermore, installing and operating plasma mirrors at high repetition rate is also costly. Here we show another direct solution using graphene as the thinnest and strongest target ever made. We develop a facile transfer method to fabricate large-area suspended graphene (LSG) as target for laser ion acceleration with precision down to a single atomic layer. Direct irradiation of the LSG targets with an ultra intense laser generates energetic carbons and protons evidently showing the durability of graphene without plasma mirror. This extends the new frontier of science on graphene under extreme electromagnetic field, such as energy frontier and nuclear fusion.


1991 ◽  
Vol 69 (1) ◽  
pp. 70-76 ◽  
Author(s):  
Christopher Owen Bender ◽  
Dean Sutherland Clyne ◽  
Douglas Dolman

The title compound (10) was prepared, along with the 4-cyano isomer (11), by the direct irradiation of 5-cyanobenzocyclooctatetraene (9); the yields were 82% (Φ10 = 0.0030) and 12% (Φ11 = 0.0004) respectively. Triene 10 was thermally and photochemically reactive. Heating solutions of 10 at 150 °C for 1 h gave COT 9 quantitatively. On direct irradiation 10 forms 5-cyanobenzosemibullvalene (12; 5%, Φ = 0.019), COT 9 (70%, Φ = 0.56), and 1-cyanonaphthalene (14%, Φ = 0.078). Sensitized irradiation of 10 gave 9 exclusively (92%, Φ = 0.88). COT 9 was also produced by the direct irradiation of semibullvalene 12 (75%, Φ = 0.13). Studies with deuterium labelled 10 suggest that the photoformation of COT 9 involves a simple electrocyclic opening of the cyclobutene ring of the triene. Additionally, the labelling results indicate that the formation of semibullvalene 12 from 10 derives from the operation of two reaction pathways, the major one of which appears to be a Zimmerman di-π-methane rearrangement. The mechanism proposed for the minor pathway to 12 has not been observed in other bicyclo[4.2.0]octatrienes. Key words: mechanisms, rearrangements, photochemistry, di-π-methane.


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