Photochemical dimerisation in crystalline anthracenes

Craig, D. P.; Sarti‐Fantoni, P.

doi:10.1039/c19660000742

Cited by 29 publications

(25 citation statements)

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“…Following the literature, 9‐substituted anthracene derivatives which are found to react under irradiation largely obey the topochemical principle, with the noticeable exception of 9‐cyano‐anthracene . The 9MA system follows the general rule and, as both observed in all the previous experiments and in the present work, only the trans dimer is formed in the solid state, as a consequence of the head‐to‐tail arrangement of the monomer pairs in the reactant lattice.…”

Section: Introductionsupporting

confidence: 79%

Solid-state photodimerization of 9-methyl-anthracene

Salzillo

Venuti

Valle

et al. 2016

J. Raman Spectrosc.

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Raman microscopy has been used to study the crystal‐to‐crystal photodimerization of 9‐methyl‐anthracene, analyzing the time evolution of both the molecular and the lattice phonon spectra during the transformation from the reactant to the product. This has made possible the concomitant detection of the chemical and crystal lattice changes in the same portion of the irradiated crystal. The topochemical mechanism of this reaction produces a fast process leading to a complete transformation of the monomer into the dimer. Copyright © 2016 John Wiley & Sons, Ltd.

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Section: Introductionsupporting

confidence: 79%

Solid-state photodimerization of 9-methyl-anthracene

Salzillo

Venuti

Valle

et al. 2016

J. Raman Spectrosc.

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“…As discussed above for dimer 3, the product from a reaction in a crystalline solid is sometimes very different from that predicted by applying the topochemical A famous example is the photodimerization of 9-cyanoanthracene [5,14,15]. From the crystal structure of 9-cyanoanthracene, the mirror-symmetric dimer would be expected if the dimerization reaction obeyed the topochemical principle, whereas it is the centrosymmetric dimer that is actually produced.…”

Section: Introductionmentioning

confidence: 96%

Probing chemical transformations in organic solids via NMR techniques: The solid-state photodimerization reaction of 7-methoxy-4-methylcoumarin

1994

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It has been reported that crystalline 7-methoxy-4-methylcoumarin undergoes a [2 + 2] photodimerization reaction to give two different products; the major product is the syn head-head dimer, whereas the minor product is the syn head-tail dimer. In this paper, high-resolution solid-state 13C NMR and solution-state IH and ~3C NMR techniques have been applied to investigate various structural issues relating to this solid-state photodimerization reaction. In particular, spectra have been recorded at various stages during the progress of the photodimerization reaction with the aim of charting the structural changes in the system as a function of reaction progress, with particular interest in assessing the potential of this technique for investigating the structural reasons for the production of the minor product. Conformational and dynamic properties of the product obtained in this solid-state photodimerization reaction have also been assessed.

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“…Stevens has reported the formation of a solid -state dimer from 9-cyanoanthracene [35] and from 1-chloroanthracene [36], the dimer of the former being identical with the (head-to-tail) solution dimer. One of us noted the formation of a solid -state dimer from 9 -anthraldehyde [34]; Craig and Sarti-Fantoni [18] repeated the solid-state dimerisation of the aldehyde and the nitrile, rechecked the small dipole moments of these two dimers, and confirmed the head-to-tail configuration. Since the two monomers crystallise in unit cells with shortest axes of 4.3 [39] and 3.9 [32] A respectively, it was claimed that their photodimerisation did not follow the topochemical rules.…”

Section: Introductionmentioning

confidence: 99%

Topochemistry. Part XXXIII. The Solid‐State Photochemistry of Some Anthracene Derivatives

Heller

Schmidt

1971

Israel Journal of Chemistry

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The solid -state photochemistry of several substituted anthracenes has been investigated with particular reference to the behaviour of polymorphic forms of the monomers. A class of 9-substituted anthracenes (methyl, methoxycatbonyl, chloro, bromo) crystallising in antiparallel, sandwich packing arrangements give centrosymmemc dianthracenes in accordance with the topochemical~inciple, which also operates on light-stable monomers packing in non-centrosymmetric space groups having axes >8 A(e. g. 9-methoxy, 9-ethoxy-, t-cyano-) and showing no short parallel interplanar contacts. Some but not all monomers, crystallising in the parallel-stack rype with a 4A axis, dimerise to the non-topochemical head-to-tail dirner, Two monomers substituted elsewhere than in the 9-position give the theoretical number of solution dimers but yield only one dimer in the solid state. IntroductionPrevious papers in this series have considered the relation between crystallattice geometry of a monomer, its solid-state photoreactivity, and the configuration of the (cyclic) photodimer. The present communication extends this topochemical study from the C 4-cyclisation of d,l3-unsaturated acids, etc., to the solid-state dimerisation of anthracenes (Cs-cyclisation).When this work was begun information on the solid -state photochemistry of anthracene derivatives was scant; however, solution photodimerisation of 1-,2-, and 9-substituted anthracenes had been studied intensively by several schools [3. 9. 15.42). The dimers have been assigned the head-totail configuration on the basis of dipole-moment measurements [2. 14) and chemical correlation [1. 13.23). No completely satisfactory explanation for the formation of only one of the two possible dimers from 9-substituted anthracenes has been given. The failure of head-to-head dimerisation has been put down to steric factors. Head-to-tail dimers from (unsymmetrically substituted) 9. 10-derivatives have been described [12.44) as well as crossdimers between 9. 10-disubstituted anthracenes and anthracene [5.40) • For parr XXXII, see Ref. 7• •• Deceased.

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Photochemical dimerisation in crystalline anthracenes

Cited by 29 publications

References 0 publications

Solid-state photodimerization of 9-methyl-anthracene

Solid-state photodimerization of 9-methyl-anthracene

Probing chemical transformations in organic solids via NMR techniques: The solid-state photodimerization reaction of 7-methoxy-4-methylcoumarin

Topochemistry. Part XXXIII. The Solid‐State Photochemistry of Some Anthracene Derivatives

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