Tetrathiafulvalene belts with large cavities

Angewandte Chemie - International Edition

Volumn 38, Issue 10, 1999, Pages 1417-1420

  Simonsen, Klaus B ^a   Svenstrup, Niels ^a   Lau, Jesper ^a   Thorup, Niels ^b   Becher, Jan ^a  

^a UNIVERSITY OF SOUTHERN DENMARK   (Denmark)

^b TECHNICAL UNIVERSITY OF DENMARK   (Denmark)

Author keywords

Cyclophanes; Macrocycles; Solid state structures; Supramolecular chemistry; Tetrathiafulvalenes

Indexed keywords

TETRATHIAFULVALENE DERIVATIVE;

ARTICLE; CARBON NUCLEAR MAGNETIC RESONANCE; CHROMATOGRAPHY; ELECTROCHEMICAL ANALYSIS; ELECTROCHEMISTRY; MASS SPECTROMETRY; OXIDATION REDUCTION REACTION; STEREOISOMERISM; SYNTHESIS;

EID: 0033577823     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/(SICI)1521-3773(19990517)38:10<1417::AID-ANIE1417>3.0.CO;2-3     Document Type: Article

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45. The 2-cyanoethyl group is cleaved in preference to the 2-(4-nitrophenyl)ethyl group upon exposure to cesium hydroxide. Therefore a stepwise cleavage can be performed by slow addition of the base in four subsequent steps.
46. [13] by heating a 1:1 mixture of 4,5-bis(2-cyanoethylthio)-1,3-dithiole-2-one and 4,5-bis[2-(4-nitrophenyl)ethylthio]-13-dithiole-2-thione in freshly distilled triethylphosphite. Experimental details of the synthesis of 1 and 2 a-c will be reported elsewhere.
47. 13C NMR), spectrometric data (PD-MS), cyclic voltammetries, and elemental analyses.
48. The intermediate compounds 3-5 as well as the final TTF-belts 6 can be manipulated in air without any precautions; this is in contrast to the case for a number of other bis-TTF sandwiches. This is probably a consequence of the rigidity of the belts, which prevents intramolecular interactions between the two redox-active units, which is known to lower the redox potential.
49. The latter isomer is chiral, but no attempt to separate the two enantiomers was carried out.
50. int = 0.0664. Structure solution and refinement and production of the crystallographic illustrations was carried out with the Siemens SHELXTL package (G. M. Sheldrick, SHELXTL Users Manual, Version 5.0, Siemens Analytical X-ray Instruments Inc., Madison, WI, USA, 1994) and SHELX-97
51. -3. Crystallographic data (excluding structure factors) for the structure reported in this paper have been deposited with the Cambridge Crystallographic Data Centre as supplementary publication no. CCDC-115-498. Copies of the data can be obtained free of charge on application to CCDC, 12 Union Road, Cambridge CB2 1EZ, UK (fax: (+44)1223-336-033; e-mail: deposit@ccdc.cam.ac.uk).