128315-73-1Relevant articles and documents
Donor-π-acceptor species derived from functionalised 1,3-dithiol-2- ylidene anthracene donor units exhibiting photoinduced electron transfer properties: Spectroscopic, electrochemical, X-ray crystallographic and theoretical studies
Batsanov, Andrei S.,Bryce, Martin R.,Coffin, Malcolm A.,Green, Andrew,Hester, Ronald E.,Howard, Judith A. K.,Lednev, Igor K.,Marti?n, Nazario,Moore, Adrian J.,Moore, John N.,Orti?, Enrique,Sa?nchez, Luis,Saviro?n, Mari?a,Viruela, Pedro M.,Viruela, Rafael,Ye, Tian-Qing
, p. 2580 - 2592 (2007/10/03)
Novel single-component donor-acceptor species 7 and 8 have been synthesised from substituted 10-(1,3-dithiol-2-ylidene)anthracen-9(10H)one 6 by reaction with Lehnert's reagent and with N,N'- bis(trimethylsilyl)carbodiimide, respectively. The steady-state UV/visible spectra of these systems contain a solvatochromic band arising from intramolecular charge transfer between the donor and acceptor groups. Ultrafast time-resolved spectroscopy shows that the excited state formed on photolysis has a lifetime of 170-400 ps, which depends strongly on solvent polarity. Cyclic voltammetric data indicate the presence of two active redox centres in the molecules: electrochemical oxidation and reduction form cation radicals and anion radicals, respectively. The X-ray crystal structures of compounds 6a, 7b and 11a reveal that all three molecules are severely distorted from planarity, with the central ring of the anthracenediylidene moiety adopting a boat conformation. The molecular structures of 6, 7, and 11 have been investigated theoretically at the ab initio 631G(*) level. Calculated geometries are in good agreement with the X-ray data and clearly show the decrease in steric hindrance along the series 11 > 7 > 8 > 6. The calculations support the intramolecular charge-transfer nature of the lowest energy absorption band observed for 6, 7 and 8, and explain the origin of the redox properties for these compounds. The optimised geometries of the cation radical, anion radical and dianion of compound 7 illustrate the structural changes induced by the charging process. For the dianion, the steric interactions are alleviated by rotation of the acceptor dicyanomethylene unit, but the presence of the donor dithiole group hinders the achievement of a fully aromatic planar structure for the central anthracene skeleton.
Highly Conjugated ?-Electron Donors for Organic Metals: Synthesis and Redox Chemistry of New 1,3-Dithiole and 1,3-Selenathiole Derivatives
Moore, Adrian J.,Bryce, Martin R.
, p. 157 - 168 (2007/10/02)
The bis(1,3-dithiolium) dication salts 8a-c have been synthesised in three steps (31-51percent overall yields) starting from 1,4-bis(bromomethyl)naphthalene, 9,10-bis(chloromethyl)anthracene and 4,4'-bis(chloromethyl)biphenyl, respectively.The bis(halogenomethyl) compounds 5 were converted into the dipiperidiniumbis(dithiocarboxylate) salts 6, which on alkylation with 3-chlorobutan-2-one yielded bis(dithioesters) 7; cyclisation of 7 occurred on treatment with concentrated sulphuric acid to give dication salts 8.Dimethyl 1,3-dithiol-2-ylphosphonate 20, dimethyl 4,5-dimethyl-1,3-dithiol-2-ylphosphonate 21 and dimethyl 1,3-selenathiol-2-ylphosphonate 22 were treated with butyllithium in the presence of a range of carbonyl compounds and quinones, e.g., cyclopentanone, cyclohexanone, benzophenone, acetophenone, benzaldehyde, thioxanthen-9-one, anthraquinone, bianthrone and naphthacene-5,12-quinone to yield Wittig-Horner products, e.g., alkenes 26-34 and the anthracenediylidene derivatives 35, 36, 40-43 and 53.Unsymmetrical derivatives 37-39 were prepared in two steps as follows: anthrone reacted with 2-methylthio-1,3-dithiolium iodides 45 and 46 in pyridine-acetic acid to yield ketones 48 and 49 which were then treated with the Wittig-Horner reagents 23-25.Cyclic voltammetric data for the new tetrathiafulvalene, selenatrithiafulvalene and diselenadithiafulvalene derivatives 35-43 and 53, show that these systems undergo two-electron redox behaviour which is observed as a single wave.Complexes of these donors with electron acceptors, e.g. 7,7,8,8-tetracyano-p-quinodimethane (TCNQ), have been obtained, some of which are organic semiconductors.
Unsymmetrical and Highly-conjugated Tetrathiafulvalene and Selenatrithiafulvalene Derivatives: Synthesis and Reactions of Novel Heterocyclic Wittig-Horner Reagents
Bryce, Martin R.,Moore, Adrian J.,Lorcy, Dominique,Dhindsa, Ajaib S.,Robert, Albert
, p. 470 - 472 (2007/10/02)
Novel 1,3-dithiole 1-selena-3-thiole Wittig-Horner reagents have been developed and used in the efficient synthesis of a range of new, unsymmetrical tetrathiafulvalene and selenatrithiafulvalene derivatives (6)-(10) and (16); cyclic voltammetry establishe
