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Lookup NU author(s): Professor Andrew Benniston,
Emeritus Professor Bill Clegg
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Absorption and electrochemical properties are reported for the iron(II) complex of the unusually substituted ligand 3,3″-bis(4-methylphenyl)-2,2′:6′,2″-terpyridine, along with the structure determination of the complex by single-crystal X-ray crystallography. Crystal data for C67H64.5F12FeN7.5OP2, M 1336.6: triclinic, a 12.768(3), b 15.789(4), c 17.160(4) Å, α 85.553(6), β 77.756(6), γ 66.754(5)°, F3106.1(12) Å3, space group P 1 Z 2, p 1.43 g cm-3, μ 0.30 mm-1 for γ 0.6849 Å, R 0.091 for 4456 observed (I > 2σ(I)) reflections, wR2 0.241, Δp±1.68 e Å-3. The structural analysis reveals that, as observed in analogous bisterpyridineiron(n) complexes, the ligands adopt the preferred meridional binding motif. As a result, the 'pulling-in' of the outer pyridine rings forces each pair of 3,3″ substituted tolyl groups to diverge, resulting in an average distance between the tolyl methyl groups of c. 11.6 Å. The cyclic voltammetery of the complex in MeCN displays upon oxidative scanning a reversible one-electron wave (E° = + 0.99 V v. s.c.e.) and three one-electron waves under reducing conditions (E1° = -1.27 V, E2° = -1.51 V, E3° = -1.96 V v. s.c.e.). The electronic spectrum in acetonitrile contained an MLCT band centred at 571 nm, with a molar absorption coefficient of 18210 M-1 cm-1. When compared to similar phenyl-substituted terpyridine ligand iron(II) complexes this is a relatively low value and is assigned to reduced electronic delocalization throughout the terpyridine backbone. © CSIRO 2000.
Author(s): Benniston AC, Farrugia LJ, Mackie PR, Mallinson P, Clegg W, Teat SJ
Publication type: Article
Publication status: Published
Journal: Australian Journal of Chemistry
Print publication date: 01/01/2000
ISSN (print): 0004-9425
ISSN (electronic): 1445-0038
Publisher: CSIRO Publishing
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