Hydrogen bonded anion ribbons, networks and clusters and sulfur–anion interactions in novel radical cation salts of BEDT-TTF with sulfamate, pentaborate and bromide

Andrew C. Brooks; Lee Martin; Peter Day; Elsa B. Lopes; Manuel Almeida; Koichi Kikuchi; Wataru Fujita; Kota Sasamori; Hiroki Aktusu; John D. Wallis

doi:10.1039/C3DT32430C

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Dalton Transactions

Issue 18, 2013

The international journal for inorganic, organometallic and bioinorganic chemistry

Impact Factor 3.838 48 Issues per Year Indexed in MEDLINE

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Paper

Hydrogen bonded anion ribbons, networks and clusters and sulfur–anion interactions in novel radical cation salts of BEDT-TTF with sulfamate, pentaborate and bromide

Andrew C. Brooks,^a^b Lee Martin,^a Peter Day,^b Elsa B. Lopes,^c Manuel Almeida,^c Koichi Kikuchi,^d Wataru Fujita,^d Kota Sasamori,^d Hiroki Aktusu^e and John D. Wallis*^a

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Corresponding authors

School of Science and Technology, Nottingham Trent University, Clifton Lane, Nottingham NG11 8NS, UK
E-mail: john.wallis@ntu.ac.uk

University College London, Department of Chemistry, 20 Gordon Street, London WC1H 0AJ, UK

Department Química, IST/ITN, Instituto Superior Técnico/CFMCUL, P-2686-953 Sacavém, Portugal

Department of Chemistry, Tokyo Metropolitan University, Hachioji, Japan

Graduate School of Material Science, University of Hyogo, Kamigori-cho, Ako-gun, Japan

Dalton Trans., 2013,42, 6645-6654

DOI: 10.1039/C3DT32430C
Received 11 Oct 2012, Accepted 26 Feb 2013
First published online 28 Feb 2013

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Abstract
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The novel radical cation salt (BEDT-TTF)₃(sulfamate)₂·2H₂O (BEDT-TTF = bis(ethylenedithio)tetrathiafulvalene) is semiconducting with donor stacks comprised of pairs of partially oxidized molecules and a single more highly oxidized molecule which is twisted out of the stack by ca. 30°. Hydrogen bonded pairs of sulfamate ions are linked into parallel ribbons by further hydrogen bonding between sulfamates and bridging water molecules. In contrast, the BEDT-TTF salt with pentaborate contains infinite layers formed of a network of hydrogen bonded pentaborate anions. Two new bromide salts of BEDT-TTF are reported, one is a semiconducting 1:1 salt in which the bromide is integrated among the BEDT-TTF donors, while the other contain a square of four bromide ions linked together by hydrogen bonding to a centrally located H₅O₂⁺ cation for every five BEDT-TTF molecules.