Jarrod H. N. Buttery, Effendy, Siti Mutrofin, Neil C. Plackett, Brian W. Skelton, Claire R. Whitaker, Allan H. White
The present and three subsequent papers describe the syntheses and structural characterization of crystalline adducts, sometimes solvated, obtained from (usually methanolic) solutions of simple group 1 metal salts, MX, with the N,N′-aromatic bases L = 2,2′-bipyridine ('bpy'), 1,10-phenanthroline ('phen') and 2,9-dimethyl,1,10-phenanthroline ('dmp') of 1:n (n = 1,2,3 and some non-integral) stoichiometries and anhydrous conditions. X are predominantly weakly basic oxyanions ClO4, NO3, O 3SCF3 (= 'triflate', 'tfs') and (pseudo-) halides for M = Li, Na, K, Rb (not, as yet, 'tfs'). The present paper describes adducts of 1:1 (or near 1:1) MX : L stoichiometry. The majority of arrays described are single-stranded one-dimensional linear polymers, LM units being bridged by oxyanions: single-stranded LiNO3: dmp (1:1) (∞|∞), (the Na analogue is isomorphous, but with a different anion bonding mode), and double-stranded NaClO4: bpy (1:1)(∞|∞) and Mtfs: dmp (1:1)(∞|∞) (M = Na, K, Rb): an interesting single-stranded 'hydrolysis' product, with supernumerary interleaving phen moieties 'solvating' as well as methanol, is defined as NaI: phen: H2O: MeOH (1:1(+1):2:1), [(phen)Na(μ-OH2) 2](∞|∞)I·phen·MeOH. The complex LiCl : dmp (2:2) is a dimer, [(dmp)Li(μ-Cl)2Li(dmp)], while the LiBr : dmp system is defined in terms of two ionic adductsLiBr : dmp : MeOH (1:1:2.5) = [(dmp)Li(HOMe)2]Br· 0.5MeOH and LiBr : dmp : MeOH : H2O (1:1(+1):1:1), 'solvated' with dmp, MeOH and H2O, as [(dmp)Li(HOMe)(OH2)]Br-dmp; also of this family is LiNCS : dmp : MeOH (1:1:1) ≡ [(dmp)Li(yVCS)(HOMe)]. The adduct KPF6 : dmp (1:1)(∞|∞), is a novel double-stranded one-dimensional polymer in which (dmp)K units are bridged by PF6 counterions. Ktfs : dmp : MeOH (2:2:1)2 is a complex tetramer in which all species are coordinated, but its rubidium counterpart is an infinite polymer. Of more complex stoichiometry are the adducts KI : dmp : MeOH (6:8:3) = [K 6I4(dmp)8]I2·3MeOH containing a 'polyiodide' cation, and Ktfs : dmp (4:3), a double-stranded, one-dimensional polymer. © 2006 WILEY-VCH Verlag GmbH & Co. KGaA.
University of Western Australia, Chemistry M313, School of Biomedical, Biomolecular and Chemical Sciences, Crawley, WA 6009, Australia; FMIPA Universitas Negeri Malang, Jurusan Pendidikan Kimia, Malang 65145, Jalan Surabaya 6, Indonesia; Chemistry M313, University of Western Australia, Crawley, WA 6009, Australia
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