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Synthesis of and Charge Transfer Complexes Derived from Thianyl Tetrathiofulvalenes

IP.com Disclosure Number: IPCOM000083023D
Original Publication Date: 1975-Mar-01
Included in the Prior Art Database: 2005-Feb-28
Document File: 3 page(s) / 82K

Publishing Venue

IBM

Related People

Fukushima, AA: AUTHOR [+2]

Abstract

Described is the synthesis of the first example of thiophenefused tetrathiofulvalene compounds. These materials exhibit strong electron donation properties and yield useful conductive organic charge-transfer systems with suitable electron acceptors, such as tetracyanoquinodimethane (TCNQ).

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Synthesis of and Charge Transfer Complexes Derived from Thianyl Tetrathiofulvalenes

Described is the synthesis of the first example of thiophenefused tetrathiofulvalene compounds. These materials exhibit strong electron donation properties and yield useful conductive organic charge-transfer systems with suitable electron acceptors, such as tetracyanoquinodimethane (TCNQ).

The key step of the synthetic sequence is the cyclosulfuriztion of sigma-O- alkyl xanthate esters of gamma-butyrolactone, affording in a single step the tetrathio bicyclic carbonate.

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Xanthate esters 2 were readily prepared from commercially available sigma- chloro-gamma-butyrolactone 1. Also isolated from the complex product mixture of 3 were dehydrogenated 4, oxoderivative 5 and trithioxanthate ester 6. As shown above, thiophene derivative 4 is best obtained from 3 by sulfur dehydrogenation at 180 degrees. Byproduct 5 yields 3 on treatment with P(2)S(5). Physical properties of compounds 3, 4 ana 5 are listed in Table I.

Thiocarbonates 3 and 4 are each coupled to produce cis-trans mixtures of fused-thiophene derivatives. In the case of 4 oxidative coupling leads to cis-trans 1,1,2',2'-bis(1,2-dithiathianyl) ethylene 8 (mp 214-15, 30%), whereas compound 3 is best coupled to the tetrahydro analogue 7 by electrochemical methods.

Finally, compounds 7 and 8 function as electron donor molecules by forming charge-transfer complexes when admixed with electron accepting partners. Thus ace...