The crystal structure of bis (2,2′:6′,2″-terpyridine)iron(II) bis ( perchlorate ) hydrate has been determined by single-crystal X-ray diffractometry . The compound is monoclinic, space group P21, with two molecules in a unit cell of dimensions a 8.830(3), b 8.914(1), c 20.037(6)Ǻ, β 100.82(1)°. The structure was refined by least squares to a residual of 0.048 for 2007 observed reflections. The cation is found to have approximate D2d symmetry, with the principal distortion from octahedral symmetry being an axial compression. The lattice water molecule and anions are oriented towards the interligand pockets of the cation. There is hydrogen bonding between the water molecule and one anion.

Osmium complexes of the type [OsB2X2]n+ where B = 2,2'-bipyridine (bipy) or 1,10-phenanthroline (phen), X = Cl, Br, I, py, NH3; 2X = glycinato, acetylacetonato, ethylenediamine, oxalato, phen, or bipy and = 0, 1, 2, 3 are described. [OsB2X2]0 has the cis configuration. Usually compounds in both oxidation states (II) and (III) were stable and could be isolated. The compounds did not disproportionate and the unidentate ligands were replaced only with difficulty. The [Osbipy2phen]2+ and [Osbipyphen2]2+ ions were resolved through their (+) antimonyl tartrate salts and were found to be optically stable in both the Os(II) and Os(III) states.

The magnetic and Mossbauer spectral properties of hydrated and anhydrous complex salts [Fe( bpp )2] X2, where bpp = [2,6-bis(pyrazol-3-yl)pyridine] and X = PF6, BF4, Br, I, NO3, are indicative of a temperature-induced singlet (1A1) ↔ quintet (5T2) transition in the complex cation. The nature of the transition depends on the anion and the degree of hydration. The transition is displaced to lower temperatures in the anhydrous species and for the hydrated is only partial above room temperature. The transition in the hydrated hexafluorophosphate salt occurs in two steps, and that in the anhydrous hexafluorophosphate is incomplete, a high residual fraction of quintet state species being retained below the transition temperature. For the anhydrous complexes the transition is discontinuous and that in the complex iodide is associated with a narrow thermal hysteresis with transition temperatures Tc ↓ = 203 K and Tc ↑ = 205 K. The structures of [Fe( bpp )2]I2.4H2O and [Fe( bpp )2][BF4]2.3H2O have been determined at 298 K. Both complex salts are essentially low spin at this temperature and have an average Fe-N distance of 1.95 Ǻ. The structures reveal in both instances an extended hydrogen-bonded network involving the uncoordinated >NH groups of the ligands, the anions and lattice water. It is suggested that it is this bonding which is responsible for the favouring of the singlet state in the hydrated salts. Bis [2,6-bis(pyrazol-3-yl)pyridine]iron(II) diiodide tetrahydrate : triclinic, space group Pī , a 8.276(8), b 8.305(7), c 21.941(27) Ǻ, α 98.11(5), β 90.08(6), γ 90.82(6)°, Z 2. Bis [2,6-bis(pyrazol-3-yl)pyridine]iron(II) bis ( tetrafluoroborate ) trihydrate : monoclinic, space group C2/c, a 31.222(15), b 14.456(3), c 12.907(5) Ǻ, β 99.40(2)°, Z 8.

Iron(II) and nickel(II) [MN6]X2 type complexes have been prepared from 2-(pyrazol-1-yl]pyridine (1pp), 2-(pyrazol-1-yl) imidazoline (pi), 2- (pyrazol-3-yl)pyridine (3pp) and 2,6-bis(pyrazol-3-yl)pyridine ( bpp ). Variable-temperature magnetic and Mossbauer spectral studies establish that [Fe(1pp)3]X2 is low spin and [Fe(pi)3]X2 is high spin over an extended temperature range, while both [Fe(3pp)3]X2 and [Fe( bpp )2]X2 undergo temperature-induced low-spin ↔ high-spin transitions. The nature of the transition depends on the extent of hydration and for salts of both cations the singlet state is generally stabilized as the extent of hydration increases. Hydrogen bonding effects are believed to be responsible for this. For anhydrous [Fe( bpp )2] [BF4]2 the transition is discontinuous and associated with hysteresis with Tc ↓ 173 K for decreasing temperature and Tc ↑ 183 K for increasing temperatures. The transition to the singlet state species is complete at low temperatures provided that the cooling rate is relatively slow. Rapid cooling to 77 K results in the trapping of a fraction of metastable quintet state species. For all other species containing either [Fe(3pp)3]2+ or [Fe( bpp )2]2+ the spin transition is continuous. Spectral data for [NiN6]X2 complexes establish an order of field strengths for the ligands pi < 3pp < 1pp < bpp , which, for the bidentate species only, is consistent with the observed electronic properties of the corresponding [FeN6]X2 complexes.

Complexes of stoichiometry Fe( trzH )2( trz )X, where trzH is 1,2,4-triazole and X = BF4, ClO4, PF6, have been prepared. All three salts display temperature-induced singlet (1A1) ↔ quintet (5T2) transitions which are generally discontinuous and associated with a broad hysteresis loop. The salts are strongly thermochromic, being white above and pink-lilac below the transition region. Several samples of each salt were obtained and the detailed behaviour varied somewhat from one sample to another. For the fluoroborate and perchlorate salts the transition is centred above room temperature while for the hexafluorophosphate salt it occurs below room temperature. The perchlorate salt was also isolated in a form which showed a continuous transition but the nature of its electronic properties changed as the sample aged. In one form of the hexafluorophosphate salt the hysteresis loop spans room temperature and it has been possible to characterize both the singlet and the quintet state species at that temperature. For all three salts the transition has been characterized by measurement of the temperature dependence of the magnetism and Mossbauer and electronic spectra. These measurements establish that the complexes all contain an FeN6 coordination core and this must be achieved through bridging of the triazole units.