Phosphorus-sulfur heterocycles incorporating an O-P(S)-O or O-P(S)-S-S-P(S)-O scaffold : one-pot synthesis and crystal structure study

The authors are grateful to the University of St Andrews for financial support.A new one-pot preparative route was developed to synthesize novel organophosphorus sulfur heterocycles via the reaction of the four-membered ring thionation reagent [2,4-diferrocenyl 1,3,2,4-diathiadiphosphetane 2,4-disulfide (FcLR, a ferrocene analogue of Lawesson’s reagent)] and alkenyl/aryl-diols and I2 (or SOCl2) in the presence of triethylamine. Therefore, a series of five- to ten-membered heterocycles bearing an O-P(S)-O or an O-P(S)-S-S-P(S)-O linkage were synthesized. The synthesis features a novel application of the multicomponent reaction, providing an efficient and environmentally benign method for the preparation of the unusual phosphorus-sulfur heterocycles. Seven representative X-ray structures confirm the formation of these heterocycles.Publisher PDFPeer reviewe

Influence of s,p-d and s-p exchange couplings on exciton splitting in (Zn,Mn)O

This work presents results of near-band gap magnetooptical studies on (Zn,Mn)O epitaxial layers. We observe excitonic transitions in reflectivity and photoluminescence, that shift towards higher energies when the Mn concentration increases and split nonlinearly under the magnetic field. Excitonic shifts are determined by the s,p-d exchange coupling to magnetic ions, by the electron-hole s-p exchange, and the spin-orbit interactions. A quantitative description of the magnetoreflectivity findings indicates that the free excitons A and B are associated with the Gamma_7 and Gamma_9 valence bands, respectively, the order reversed as compared to wurtzite GaN. Furthermore, our results show that the magnitude of the giant exciton splittings, specific to dilute magnetic semiconductors, is unusual: the magnetoreflectivity data is described by an effective exchange energy N_0(beta-alpha)=+0.2+/-0.1 eV, what points to small and positive N_0 beta. It is shown that both the increase of the gap with x and the small positive value of the exchange energy N_0 beta corroborate recent theory describing the exchange splitting of the valence band in a non-perturbative way, suitable for the case of a strong p-d hybridization.Comment: 8 pages, 8 figure

A tight Erd\H{o}s-P\'osa function for wheel minors

Let $W_t$ denote the wheel on $t+1$ vertices. We prove that for every integer $t \geq 3$ there is a constant $c=c(t)$ such that for every integer $k\geq 1$ and every graph $G$, either $G$ has $k$ vertex-disjoint subgraphs each containing $W_t$ as minor, or there is a subset $X$ of at most $c k \log k$ vertices such that $G-X$ has no $W_t$ minor. This is best possible, up to the value of $c$. We conjecture that the result remains true more generally if we replace $W_t$ with any fixed planar graph $H$.Comment: 15 pages, 1 figur