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Electronic, redox and charge transport properties of an unusual hybrid structure: a bis(septithiophene) bridged by a fused tetrathiafulvalene (TTF)

Electronic, redox and charge transport properties of an unusual hybrid structure: a bis(septithiophene) bridged by a fused tetrathiafulvalene (TTF)
Electronic, redox and charge transport properties of an unusual hybrid structure: a bis(septithiophene) bridged by a fused tetrathiafulvalene (TTF)
Nucleophilic substitution reactions of N(3)P(3)Cl(4)[NH(CH(2))(3)NMe] (1) and N(3)P(3)Cl(4)[NH(CH(2))(3)O] (2) with mono-functional alcohols (methanol, 2,2,2-trifluoroethanol, phenol) and a secondary amine (pyrrolidine) were used to investigate the relationship between the incoming nucleophile and the proportions of products with substituents that are cis or trans to the spiro NH moiety. The reaction products were characterized by elemental analysis, mass spectrometry, (1)H and (31)P NMR spectroscopy and the configurational isomers by X-ray crystallography. Six products have been characterised with the substituent cis to the spiro NH group for the alcohol (methanol, phenol) and pyrrolidine derivatives of both compounds 1 and 2, compared to just one derivative with the substituent trans to the spiro NH group, that for the pyrrolidine derivative of compound 2. For each reaction the relative proportions of cis and trans isomers were determined by (31)P NMR measurements of the reaction mixtures. It was found that the reactions of compound 1 with all three alcohols and of compound 2 with methanol lead to exclusive formation of isomers with the substituent cis to the NH moiety, whereas all other reactions lead to mixtures of cis and trans isomers in different ratios under standard reaction conditions. However, when crown ether is included in the reaction medium for the reactions of compound 2 with both 2,2,2-trifluoroethanol and phenol, it is found that only cis isomers are formed. All these results are rationalised in terms of the competition between at least two effects; the cis-directing effect by hydrogen bonding of the incoming nucleophile to the spiro N-H group already present on the cyclophophazene ring and the cis-directing effect of the sodium cation coordinating to the oxygen lone pairs of the P-O moiety of the spiro ring.
1462-1469
Wright, Iain A.
42bac22f-27b2-47cb-9e41-12fb75a92b6f
Skabara, Peter J.
7138e414-7d50-41c7-933e-0bccad2fa4cd
Forgie, John C.
c7d06ee3-b033-4f78-bee4-b143c52e3ab5
Kanibolotsky, Alexander L.
ce9e994f-9860-4cb6-be07-4e82b48c1fa8
González, Blanca
7259b257-8086-4563-b6c8-01f2b2b73759
Coles, Simon J.
3116f58b-c30c-48cf-bdd5-397d1c1fecf8
Gambino, Salvatore
648bf28c-1faa-4a5e-8ed9-f8006cf0681b
Samuel, Ifor D. W.
090dc85d-c89d-4d7b-ab3b-15a7e9809229
Wright, Iain A.
42bac22f-27b2-47cb-9e41-12fb75a92b6f
Skabara, Peter J.
7138e414-7d50-41c7-933e-0bccad2fa4cd
Forgie, John C.
c7d06ee3-b033-4f78-bee4-b143c52e3ab5
Kanibolotsky, Alexander L.
ce9e994f-9860-4cb6-be07-4e82b48c1fa8
González, Blanca
7259b257-8086-4563-b6c8-01f2b2b73759
Coles, Simon J.
3116f58b-c30c-48cf-bdd5-397d1c1fecf8
Gambino, Salvatore
648bf28c-1faa-4a5e-8ed9-f8006cf0681b
Samuel, Ifor D. W.
090dc85d-c89d-4d7b-ab3b-15a7e9809229

Wright, Iain A., Skabara, Peter J., Forgie, John C., Kanibolotsky, Alexander L., González, Blanca, Coles, Simon J., Gambino, Salvatore and Samuel, Ifor D. W. (2011) Electronic, redox and charge transport properties of an unusual hybrid structure: a bis(septithiophene) bridged by a fused tetrathiafulvalene (TTF). [in special issue: Celebrating the 70th birthday of Professor Fred Wudl] Journal of Materials Chemistry, 21 (5), 1462-1469. (doi:10.1039/c0jm02293d).

Record type: Article

Abstract

Nucleophilic substitution reactions of N(3)P(3)Cl(4)[NH(CH(2))(3)NMe] (1) and N(3)P(3)Cl(4)[NH(CH(2))(3)O] (2) with mono-functional alcohols (methanol, 2,2,2-trifluoroethanol, phenol) and a secondary amine (pyrrolidine) were used to investigate the relationship between the incoming nucleophile and the proportions of products with substituents that are cis or trans to the spiro NH moiety. The reaction products were characterized by elemental analysis, mass spectrometry, (1)H and (31)P NMR spectroscopy and the configurational isomers by X-ray crystallography. Six products have been characterised with the substituent cis to the spiro NH group for the alcohol (methanol, phenol) and pyrrolidine derivatives of both compounds 1 and 2, compared to just one derivative with the substituent trans to the spiro NH group, that for the pyrrolidine derivative of compound 2. For each reaction the relative proportions of cis and trans isomers were determined by (31)P NMR measurements of the reaction mixtures. It was found that the reactions of compound 1 with all three alcohols and of compound 2 with methanol lead to exclusive formation of isomers with the substituent cis to the NH moiety, whereas all other reactions lead to mixtures of cis and trans isomers in different ratios under standard reaction conditions. However, when crown ether is included in the reaction medium for the reactions of compound 2 with both 2,2,2-trifluoroethanol and phenol, it is found that only cis isomers are formed. All these results are rationalised in terms of the competition between at least two effects; the cis-directing effect by hydrogen bonding of the incoming nucleophile to the spiro N-H group already present on the cyclophophazene ring and the cis-directing effect of the sodium cation coordinating to the oxygen lone pairs of the P-O moiety of the spiro ring.

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More information

e-pub ahead of print date: 26 October 2010
Published date: 2011
Organisations: Organic Chemistry: Synthesis, Catalysis and Flow, Chemistry, Faculty of Natural and Environmental Sciences

Identifiers

Local EPrints ID: 346128
URI: http://eprints.soton.ac.uk/id/eprint/346128
PURE UUID: 3c949516-153a-4f10-8851-4567d3d16e20
ORCID for Simon J. Coles: ORCID iD orcid.org/0000-0001-8414-9272

Catalogue record

Date deposited: 14 Jan 2013 13:42
Last modified: 18 Feb 2021 16:53

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