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The relevance of abrupt magnetic and optical transitions exhibiting bistability in spin-crossover solids has been pointed out for their potential applications in optical or memory devices. In this respect, triazole-based one-dimensional coordination polymers are widely recognized as one of the most interesting systems. The measure of the interaction among spin-crossover centers at the origin of such cooperative behavior is of paramount importance and has so far been realized through modeling of spin-crossover curves derived mostly from magnetic measurements. Here, a new series of triazole-based one-dimensional coordination polymers of formula [Fe(Rtrz)(3)](A)(2)·xH(2)O with R = methoxyethyl and A = monovalent anion has been prepared that show complete and abrupt spin-crossover phenomenon as shown by magnetic measurements. The spin-crossover transition in these and related compounds is studied by differential scanning calorimetry, and the thermodynamic excess enthalpies and entropies associated with the phenomenon are derived systematically. Then the cooperative character of the spin-crossover in these materials is quantified by use of two widely used models, so-called Slichter and Drickamer and domain models. The same procedure is applied to spin-crossover curves of similar compounds available in the literature and for which calorimetric studies have been reported. The experimental thermodynamic figures, in particular the excess enthalpies, are shown to be clearly correlated to the output parameters of both models, thus providing a direct, experimental, quantitative measure of the cooperative character of the spin-crossover phenomenon.

The influence of the counteranion on the structure and the spin-transition properties of original 1D bis(tetrazole) Fe(II) systems, namely [Fe(btzx)(3)]X(2) (X=PF(6) (-) (1), CF(3)SO(3) (-) (2) and ClO(4) (-) (3); btzx=m-xylylenebis(tetrazole)) is studied. The X-ray crystal structures of compounds 1 and 2 are described in detail. These structures present a solvent molecule encapsulated within pockets formed by btzx ligands along the 1D coordination chains. Compound 2 is shown to be the first structurally characterised alternating HS-LS 1D spin-transition system (HS=high spin, LS=low spin). The magnetic susceptibility measurements of all three compounds are compared. The degree of completion and the transition temperature are both drastically influenced by the counterion used, while surprisingly, the cooperative nature of the transition is not affected by the choice of counterion. Compounds 1 and 2 are further studied by Mössbauer spectroscopy and their distinct LIESST properties are compared.

The reaction of btzmp (1,2-bis(tetrazol-1-yl)-2-methylpropane) with Fe(ClO4)2 generates a 1D polymeric species, [Fe(mu-btzmp)2(btzmp)2](ClO4)2, showing a steep spin transition (T(1/2) / =136 K and T(1/2) / =133 K) with a 3 K thermal hysteresis. The crystal structure at 100 and 200 K reveals that, in contrast to other bistetrazole based spin-transition systems such as [Fe(endi)3](BF4)2 and [Fe(btzp)3](ClO4)2, the present compound has only two ligands bridging the metallic centres, while the other two coordination positions are occupied by two mono-coordinated (non-bridging) btzmp ligands. This peculiarity confers an unprecedented crystal packing in the series of 1D bistetrazole based polymers. The change in spin state is accompanied by an order/disorder transition of the ClO4* counterion. A careful examination of the structural changes occurring upon the spin transition indicates that this order/disorder is most likely affected by the modification of the [tetrazole-centroid]-ND-Fe angle (which is typical of bistetrazole spin-transition materials). Apart from X-ray analysis, also magnetic susceptibility, Mössbauer and UV-vis spectroscopies have been used to characterise the HS and the LS states of [Fe(mu-btzmp)2(btzmp)2](ClO4)2.

The complex [Fe(teec)6](BF4)2 (teec = chloroethyltetrazole) shows a two-step complete spin-crossover transition in the temperature range 300-90 K. Time-resolved synchrotron powder diffraction experiments have been carried out in this temperature range, and crystal structure models have been obtained from the powder patterns by using the parallel tempering technique. Of these models, the low-spin state structure at 90 K has been refined completely with Rietveld refinement. Its structural characteristics are discussed in relation to the high-spin state model and other spin-crossover compounds. The complex shows a remarkable anisotropic unit-cell parameter contraction that is dependent on the applied cooling rate. In addition, the possible important implications for the interpretation of spin-crossover behavior in terms of structural changes are discussed.

Crystal structure determination and analysis have been carried out for the two spin-crossover compounds [Fe(teeX)(6)](BF(4))(2) (teeX is haloethyltetrazole; X = I: teei; X = Br: teeb), in both their high-spin (near 300 K) and their low-spin states (T = 90 K), using high-resolution powder-diffraction data collected at the ESRF (Grenoble, France) and SPring8 (Japan) synchrotron radiation facilities. The structures of teei have been solved using various direct-space structure determination techniques (grid search, genetic algorithm and parallel tempering) and refined with the Rietveld method using geometrical restraints. In the case of teeb, a structural model was found but a full refinement was not successful because of the presence of a significant amount of an amorphous component. Analysis of the structures (space group P2(1)/c, Z = 2) and diffraction data, and the absence of phase transitions, show the overall structural similarity of these compounds and lead to the conclusion that the gradual spin-crossovers are likely to be accompanied by small structural changes only.

The striking difference in cytotoxic activity between the inactive cis-[Ru(bpy)(2)Cl(2)] and the recently reported highly cytotoxic alpha-[Ru(azpy)(2)Cl(2)] (alpha indicating the isomer in which the coordinating Cl atoms, pyridine nitrogens, and azo nitrogens are in mutual cis, trans, cis orientation) encouraged the synthesis of the mixed-ligand compound cis-[Ru(azpy)(bpy)Cl(2)]. The synthesis and characterization of the only occurring isomer, i.e., alpha-[Ru(azpy)(bpy)Cl(2)], 1 (alpha denoting the isomer in which the Cl ligands are cis related to each other and the pyridine ring of azpy is trans to the pyridine ring of bpy), are described. The solid-state structure of 1 has been determined by X-ray structure analysis. The IC(50) values obtained for several human tumor cell lines have indicated that compound 1 shows mostly a low to moderate cytotoxicity. The binding of the DNA model base 9-ethylguanine (9-EtGua) to the hydrolyzed species of 1 has been studied and compared to DNA model base binding studies of cis-[Ru(bpy)(2)Cl(2)] and alpha-[Ru(azpy)(2)Cl(2)]. The completely hydrolyzed species of 1, i.e., alpha-[Ru(azpy)(bpy)(H(2)O)(2)](2+), has been reacted with 9-EtGua in water at room temperature for 24 h. This resulted in the monofunctional binding of only one 9-EtGua, coordinated via the N7 atom. The product has been isolated as alpha-[Ru(azpy)(bpy)(9-EtGua)(H(2)O)](PF(6))(2), 2, and characterized by 2D NOESY NMR spectroscopy. The NOE data show that the 9-EtGua coordinates (under these conditions) at the position trans to the azo nitrogen atom. Surprisingly, time-dependent (1)H NMR data of the 9-EtGua adduct 2 in acetone-d(6) show an unprecedented positional shift of the 9-EtGua from the position trans to the azo nitrogen to the position trans to the bpy nitrogen atom, resulting in the adduct alpha'-[Ru(azpy)(bpy)(9-EtGua)(H(2)O)](PF(6))(2) (alpha' indicating 9-EtGua is trans to the bpy nitrogen). This positional isomerization of 9-EtGua is correlated to the cytotoxicity of 1 in comparison to both the cytotoxicity and 9-EtGua coordination of cis-[Ru(bpy)(2)Cl(2)], alpha-[Ru(azpy)(2)Cl(2)], and beta-[Ru(azpy)(2)Cl(2)]. This positional isomerization process is unprecedented in model base metal chemistry and could be of considerable biological significance.

A series of homo- and heteronuclear ruthenium and osmium polypyridyl complexes with the bridging ligands 1,3-bis(5-(2-pyridyl)-1H-1,2,4-triazol-3-yl)benzene (H(2)mL) and 1,4-bis(5-(2-pyridyl)-1H-1,2,4-triazol-3-yl)benzene (H(2)pL) are reported. The photophysical properties of these compounds are investigated, and particular attention is paid to the heteronuclear (RuOs) compounds, which exhibit dual emission. This is in contrast to phenyl-bridged polypyridine Ru-Os complexes with a similar metal-metal distance, in which the Ru emission is strongly quenched because the nature of the bridging ligand allows for an efficient through-bond coupling. The results obtained for the compounds reported here suggest that energy transfer is predominantly taking place via a dipole-dipole, Förster type, mechanism, that may dominate when through-bond coupling is weak. This is in stark contrast to ground state interaction, which is found to be critically dependent on the nature of the bridging unit employed.

The dichlorobis(2-phenylazopyridine)ruthenium(II) complexes, [Ru(azpy)(2)Cl(2)], are under renewed investigation due to their potential anticancer activity. The three most common isomers alpha-, beta- and gamma-[RuL(2)Cl(2)] with L= o-tolylazopyridine (tazpy) and 4-methyl-2-phenylazopyridine (mazpy) (alpha indicating the coordinating Cl, N(pyridine) and Nazo atoms in mutual cis, trans, cis positions, beta indicating the coordinating Cl, N(pyridine) and Nazo atoms in mutual cis, cis, cis positions, and gamma indicating the coordinating Cl, N(pyridine) and Nazo atoms in mutual trans, cis, cis positions) are synthesized and characterized by NMR spectroscopy. The molecular structures of gamma-[Ru(tazpy)(2)Cl(2)] and alpha-[Ru(mazpy)(2)Cl(2)] are determined by X-ray diffraction analysis. The IC(50) values of the geometrically isomeric [Ru(tazpy)(2)Cl(2)] and [Ru(mazpy)(2)Cl(2)] complexes compared with those of the parent [Ru(azpy)(2)Cl(2)] complexes are determined in a series of human tumour cell lines (MCF-7, EVSA-T, WIDR, IGROV, M19, A498 and H266). These data unambiguously show for all complexes the following trend: the alpha isomer shows a very high cytotoxicity, whereas the beta isomer is a factor 10 less cytotoxic. The gamma isomers of [Ru(tazpy)(2)Cl(2)] and [Ru(mazpy)(2)Cl(2)] display a very high cytotoxicity comparable to that of the gamma isomer of the parent compound [Ru(azpy)(2)Cl(2)] and to that of the alpha isomer. These biological data are of the utmost importance for a better understanding of the structure-activity relationships for the isomeric [RuL(2)Cl(2)] complexes.

Ruthenium compounds have gained large interest for their potential application as chemotherapeutic agents, and in particular the complexes of the type (X)[trans-RuCl4(dmso-S)L] (X = HL or Na, NAMI-A or NAMI, respectively, for L = imidazole) are under investigation for their antimetastatic properties. The NAMI(-A)-like compounds are prodrugs that hydrolyze in vivo, and the investigation of their hydrolytic properties is therefore important for determining the nature of the potential active species. The NAMI-A-type Ru(III) complex 1, (Hdmtp)[trans-RuCl4(dmso-S)(dmtp)] (dmtp is 5,7-dimethyl[1,2,4]triazolo[1,5-a]pyrimidine), and the corresponding sodium analogue 2, (Na)[trans-RuCl4(dmso-S)(dmtp)], were synthesized. The hydrolyses of 1 and 2 in water as well as in buffered solutions were studied, and the first hydrolysis product, [mer-RuCl3(H2O)(dmso-S)(dmtp)].H2O (3), was isolated and characterized. The molecular structures of 1 and 3 were determined by single-crystal X-ray diffraction analyses and prove the importance of the hydrogen-bonding properties of dmtp to stabilize hydrolysis products. In vitro 1 (a) is not cytotoxic on tumor cells, following challenges from 1 to 72 h and concentrations up to 100 microM, (b) inhibits matrigel invasion at 0.1 mM and MMP-9 activity with an IC50 of about 1 mM, and (c) is devoid of pronounced effects on cell distribution among cell cycle phases. In vivo compound 1, similar to NAMI-A, significantly inhibits metastasis growth in mice bearing advanced MCa mammary carcinoma tumors. In the lungs, 1 is significantly less concentrated than NAMI-A, whereas no differences between these two compounds were found in other organs such as tumor, liver, and kidney. However, 1 caused edema and necrotic areas on liver parenchyma that are more pronounced than those caused by NAMI-A. Conversely, glomerular and tubular changes on kidney are less extensive than with NAMI-A. In conclusion, 1 confirms the excellent antimetastatic properties of this class of NAMI-A-type compounds and qualifies as an interesting alternative to NAMI-A for treating human cancers.

The coordination of the antimetastatic agent NAMI-A, [H(2)im][trans-RuCl(4)(dmso-S)(Him)], (Him=imidazole; dmso=dimethyl sulfoxide), to the DNA model base 9-methyladenine (9-MeAde) was investigated in water. NMR spectroscopy was first applied for the study of the molecular stability and hydrolysis of NAMI-A in aqueous solution over a range of pH (3.0-7.4) and chloride ion concentrations (0-1 M) at 37.0 degrees C. In physiological conditions (phosphate buffer, pH 7.4) NAMI-A disappears from the solution in 15 min due to chloride and dmso hydrolysis, leading to uncharacterised poly-oxo Ru species. Conversely, at lower pH (3.0-6.0) and in water (pH approximately 5.5), only a partial dmso hydrolysis occurs, slowly forming the [trans-RuCl(4)(H(2)O)(Him)](-) complex. This latter species coordinates to 9-MeAde (via the N7 of 9-MeAde), forming the [trans-RuCl(4)(9-MeAde)(Him)](-) complex. NAMI-A and [trans-RuCl(4)(H(2)O)(Him)](-) give comparable intracellular ruthenium concentrations and accumulate in KB cells (human mouth carcinoma) and accumulate these at the G(2)/M phase, while poly-oxo Ru species do not, and their cell uptake is reduced to 50%. On the contrary, G(2)/M arrest and protein content in the murine metastatic cell line metGM, are not influenced by NAMI-A hydrolysis. Hydrolysed NAMI-A species apparently are easier taken up by the metGM cells, showing intracellular ruthenium concentrations one order of magnitude greater than those of intact NAMI-A. Therefore, it is proposed that the selective antimetastatic activity of NAMI-A during in vivo experiments can be attributed to its hydrolysed species.

New water-soluble bis(2-phenylazopyridine)ruthenium(II) complexes, all derivatives of the highly cytotoxic alpha-[Ru(azpy)(2)Cl(2)] (alpha denoting the coordinating pairs Cl, N(py), and N(azo) as cis, trans, cis, respectively) have been developed. The compounds 1,1-cyclobutanedicarboxylatobis(2-phenylazopyridine)ruthenium(II), alpha-[Ru(azpy)(2)(cbdca-O,O')] (1), oxalatobis(2-phenylazopyridine)ruthenium(II), alpha-[Ru(azpy)(2)(ox)] (2), and malonatobis(2-phenylazopyridine)ruthenium(II), alpha-[Ru(azpy)(2)(mal)] (3), have been synthesized and fully characterized. X-ray analyses of 1 and 2 are reported, and compound 1 is the first example in which the cbdca ligand is coordinated to a ruthenium center. The cytotoxicity of this series of water-soluble bis(2-phenylazopyridine) complexes has been determined in A2780 human ovarian carcinoma and A2780cisR, the corresponding cisplatin-resistant cell line. For comparison reasons, the cytotoxicity of the complexes alpha-[Ru(azpy)(2)Cl(2)], alpha-[Ru(azpy)(2)(NO(3))(2)], beta-[Ru(azpy)(2)Cl(2)] (beta indicating the coordinating pairs Cl, N(py), and N(azo) as cis, cis, cis, respectively), and beta-[Ru(azpy)(2)(NO(3))(2)] have been determined in this cell line. All the bis(2-phenylazopyridine)ruthenium(II) compounds display a promising cytotoxicity in the A2780 cell line (IC(50) = 0.9-10 microM), with an activity comparable to that of cisplatin and even higher than the activity of carboplatin. Interestingly, the IC(50) values of this series of ruthenium compounds (except the beta isomeric compounds) are similar in the cisplatin-resistant A2780cisR cell line compared to the normal cell line A2780, suggesting that the activity of these compounds might not be influenced by the multifactorial resistance mechanism that affect platinum anticancer agents.

Two new isostructural compounds, dichlorobis(1-(2-chloroethyl)tetrazole)copper(II) (1) and dibromobis(1-(2-chloroethyl)tetrazole)copper(II) (2), have been prepared. The synthesis, characterization, and spectral and magnetic properties as well as the crystal and molecular structures of 1 and 2 have been studied. Both complexes form two-dimensional, distorted square grid planes of copper and halides, distinctly separated by layers of tetrazole ligands. The differential (ac) magnetic susceptibility, chi = (deltaM/deltaH)(T), and magnetization M(H) of both complexes have been studied as a function of temperature and field. The compounds possess a ferromagnetic interaction within the isolated copper-halide layers (J/k(B) = 8.0 K, J/k(B) = 10.2 K, respectively, for the chloride and the bromide, and T(c) = 4.75 K, T(c) = 8.01 K). The magnetic coupling J'/k(B) between the different layers is found to be very weak (|J'/J|

New copper(II) complexes of the cyclic trinuclear type with 1,2,4-triazole ligands, [Cu(3)(mu(3)-OH)(aaat)(3)(H(2)O)(3)](NO(3))(2).H(2)O [Haaat = 3-acetylamino-5-amino-1,2,4-triazole] (1) and ([Cu(3)(mu(3)-OH)(aat)(3)(mu(3)-SO(4))].6H(2)O)(n) [Haat = 3-acetylamino-1,2,4-triazole] (2), have been prepared and characterized by X-ray crystallography and magnetic measurements. Compound 1, the first reported with the ligand (H)aaat, consists of discrete trinuclear cations, associated NO(3)(-) anions and lattice water molecules. Compound 2 consists of unusual chains of trinuclear units with a tridentate sulfato group linking the trimeric units and water molecules stabilizing the crystal lattice. In both complexes, 1 and 2, the trinuclear [Cu(3)(OH)L(3)] unit contains a pyramidal Cu(3)-mu(3)OH core, and an almost flat Cu(3)N(6) ring formed by the N,N-bridging triazolato groups. The Cu...Cu' intratrimeric distances are 3.35-3.37-3.39 A in 1 and 3.34-3.34-3.36 A in 2. The copper atoms are five-coordinated with a distorted square-pyramidal geometry. Magnetic measurements have been performed in the 1.9-300 K temperature range. In the high-temperature region (T > 90 K), experimental data could be satisfactorily reproduced by using an isotropic exchange model, H = -J(S(1)S(2) + S(2)S(3) + S(1)S(3)), with J = -194.6 cm(-1) and g = 2.08 for 1, and J = -185.1 cm(-1) and g = 2.10 for 2. The magnitude of the antiferromagnetic exchange in both complexes is discussed on the basis of their structural features by comparison with reported N,N-pheripherically bridged trinuclear systems. In order to fit the experimental magnetic data at low temperature, an antisymmetric exchange term, H(AS) = G(S(1)xS(2) + S(2)xS(3) + S(1)xS(3)), had to be introduced, with G = 27.8 (1) and 31.0 (2) cm(-1). Crystal data: C(12)H(27)Cu(3)N(17)O(14) (1) (MW = 824.13) crystallizes in the triclinic space group, P(-)1, Z = 2, with the cell dimensions a = 8.852(2) A, b = 11.491(3) A, c = 15.404(3) A, alpha = 70.43(3) degrees, beta = 75.11(2) degrees, gamma = 88.43(2) degrees, and V = 1423.8(5) A(3), D(calcd) = 1.922 g cm(-)(3); the final agreement values were R1 = 0.0822 and wR2 = 0.2300 for 4989 unique reflections. C(12)H(28)Cu(3)N(12)O(14)S (2) (MW = 787.14) crystallizes in the triclinic space group, P(-)1, Z = 2, with the cell dimensions a = 7.146(6) A, b = 14.26(1) A, c = 15.35(2) A, alpha = 109.0(9) degrees, beta = 93.6(9) degrees, gamma = 99.5(7) degrees, and V = 1448(2) A(3), D(calcd) = 1.806 g cm(-3); the final agreement values were R1 = 0.0628 and wR2 = 0.1571 for 3997 "observed" reflections.

The title compound, tris[2-(4,5-dihydrooxazol-2-yl-kappa N)phenolato-kappa O]iron(III), [Fe(C(9)H(8)NO(2))(3)], is disordered over a non-crystallographic twofold rotation axis perpendicular to the crystallographic threefold rotation axis. The disorder can be a pure rotational disorder of an iron complex in the facial configuration, or the consequence of a mixture of facial and meridional configurations. In the latter case, at least 25% of the iron complexes must adopt the facial configuration in order to obtain the disorder ratio observed in the crystal.

In the title complex, [Cu(BF(4))(2)(1tpc)(4)] [1tpc is 1-(3-chloropropyl)-1,2,4-triazole, C(5)H(8)ClN(3)], the copper(II) centres reside in a tetragonally distorted octahedral coordination environment. Four 1tpc ligands are coordinated to the metal atom via the N4 atom of the triazole rings in a square-planar arrangement, with Cu-N bond lengths in the range 2.002 (2)-2.019 (2) A. Two tetrafluoroborate anions, in the axial positions above and below the square plane, are weakly coordinated to the copper(II) centre, with Cu-F distances of 2.4009 (18) and 2.5096 (18) A.

The structure of the coordination compound [Fe(teec)(6)](BF(4))(2), hexa[1-(2-chloroethyl)tetrazole]iron(II) di(borotetrafluoride), has been determined using the grid-search techniques of the program suite MRIA. A Guinier-camera data set was used to determine the unit cell, the space group and to position the initial model. A high-resolution synchrotron powder data set was used to position a more detailed model using torsion-angle variation and to refine the structure leading to Rp = 0.0689, Rw = 0.0805 and GoF = 1.38. The crystal structure at room temperature shows the existence of two symmetry-equivalent iron(II) ions in the high-spin state.

In this paper are presented the syntheses, characterizations, and dynamic solution behaviors of three cis-[Ru(bpy)2(L)2] (bpy = 2,2'-bipyridine) complexes, 1-3, in which L represents the monodentate ligands 1-methylimidazole (MeIm), 1,2-dimethylimidazole (Me2Im), and 1-methylbenzimidazole (MeBim), respectively. Because of their different steric properties, these three monodentate ligands yield complexes that show quite different fluxional behaviors in solution. These behaviors are studied with several 1H NMR techniques at various temperatures between -95 and degrees C. The 1H NMR spectra of 1, which has the smallest monodentate ligand of the three used, indicate the complex to be in fast exchange (i.e., the imidazoles rotate around their Ru-N axes) at all recording temperatures. The sterically more demanding ligands, Me2Im and MeBim, in 2 and 3, respectively, are in fast exchange at 55 degrees C and in slow exchange at low temperatures, showing three different atropisomers: two head-to-tail (HT) isomers and one head-to-head (HH) isomer. The newly synthesized bidentate ligand 1,2-bis-(1-methyl-2-benzimidazolyl)ethane (mdbz) forms the complex cis-[Ru(bpy)2(mdbz)](PF6)2 (4), in which the two benzimidazole moieties are constrained and relatively fixed. The two tethered benzimidazoles in 4 cannot rotate around their Ru-N axes, and therefore 4 is a good model for the main HT isomer of 3.

The synthesis and characterization of alpha-[Ru(azpy)2(NO3)2], 1, are reported (azpy is 2-(phenylazo)pyridine; alpha indicates the isomer in which the coordinating pairs ONO2, N(py), and N(azo) are cis, trans, and cis, respectively). The solid-state structure of 1 has been determined by X-ray crystallography. Crystal data: orthorhombic a = 15.423(5) A, b = 14.034(5) A, c = 10.970(5) A, V = 2374(2) A3, space group P2(1)2(1)2(1) (No. 19), Z = 4, Dcalc = 1.655 g cm-3. The structure refinement converged at R1 = 0.042 and wR2 = 0.118 for 3615 unique reflections and 337 parameters. The octahedral complex shows monodentate coordination of the two nitrate ligands. The Ru-N(azo) bond distances (2.014(4) and 1.960(4) A), slightly shorter than the Ru-N(py) bonds (2.031(4) and 2.059(4) A), agree well with the pi-back-bonding ability of the azo groups. The binding of the DNA-model bases 9-ethylguanine (9egua) and guanosine (guo) to 1 has been studied and compared with previously obtained results for the binding of model bases to the bis(bipyridyl)ruthenium(II) complex. The ligands 9egua and guo appear to form monofunctional adducts, which have been isolated as alpha-[Ru(azpy)2(9egua)Cl]PF6, 2, alpha-[Ru(azpy)2(9egua)(H2O)]-(PF6)2, 3, alpha-[Ru(azpy)2(guo)(H2O)](PF6)2, 4, and alpha-[Ru(azpy)2(guo)Cl]Cl, 5. The orientations of 9egua and guo in these complexes have been determined in detail with the use of 2D NOESY NMR spectroscopy. In 2 and 5, H8 is directly pointed toward the coordinated Cl, whereas, in 3 and 4, H8 is wedged between the pyridine and phenyl rings. The guanine derivatives in the azpy complexes can have more orientations than found for related cis-[Ru(bpy)2Cl2] species. This fluxionality is considered to be important in the binding of the alpha-bis(2-(phenylazo)pyridine)ruthenium(II) complex to DNA. In complex 1, ruthenium is the chiral center and in the binding to guanosine, two diastereoisomers each of adducts 4 and 5 have been clearly identified by NMR spectroscopy.

[Fe(btzp)3](ClO4)2 (btzp = 1,2-bis(tetrazol-1-yl)propane) represents the first structurally characterized Fe(II) linear chain compound exhibiting thermal spin crossover. It shows a very gradual spin transition (T1/2 = 130 K) which has been followed by magnetic susceptibility measurements and 57Fe Mössbauer spectroscopy. The structure has been solved at 200 and 100 K by single-crystal X-ray analysis. It crystallizes in the trigonal space group P3c1 with Z = 2 Fe(II) units at both temperatures. The molecular structure consists of chains running along the c axis in which the Fe(II) ions are linked by three N4,N4' coordinating bis(tetrazole) ligands. The main difference between the two forms appears to be in the Fe-N bond lengths, which are 2.164(4) A at 200 K and 2.038(4) A at 100 K. The Fe-Fe separations are 7.422(1) A at 200 K and 7.273(1) A at 100 K. The EXAFS results are consistent with the crystal structure. In both spin states, the FeN6 octahedron is almost regular within the EXAFS resolution. The Fe-N distance is found as 2.16(2) A at 300 K and 2.00(2) A at 40 K. The absence of the "7 A peak" in the EXAFS spectra of [Fe(btzp)3](ClO4)2, in contrast with what has been observed for the [Fe(4-R-1,2,4-triazole)3]-(anion)2 chain compounds, confirms that this peak can be used as the signature of a metal alignment only when it involves a strongly enhanced multiple scattering M-M-M path, with M-M spacing less than 4 A. Irradiation with green light at 5 K has led to the population of the metastable high-spin state for the iron(II) ion. The nature of the spin-crossover behavior has been discussed on the basis of the structural features.

The reaction of Haat [Haat = (3-acetylamino-1,2,4-triazole)] with aquated Cu(CF3SO3)2, Cu(NO3)2, and Cu(ClO4)2, respectively, in water results in the trinuclear complexes [Cu3(OH)(aat)3(CF3SO3)(H2O)2](CF3SO3) (1), [Cu3(OH)(aat)3(NO3)(H2O)2](NO3).(H2O)2 (2), and [Cu3(OH)(aat)3(ClO4)(H2O)2](ClO4) (3). The synthesis, X-ray structure, and magnetic and spectroscopic properties of the three title complexes are described. The cation of the three complexes is trinuclear with a Cu3OH skeleton which has the N-N diazine grouping of a triazole ring as bridge between each pair of copper atoms. The Cu3OH units have an average Cu-O distance of 1.991(6) (1), 2.000(6) (2), and 2.007(6) (3) A, an average Cu-Cu' distance of 3.355(2) (1), 3.341(1) (2), and 3.371(3) (3) A, and an average Cu-O-Cu' angle of 114.6(3) degrees (1), 112.4(2) degrees (2), and 115.4(3) degrees (3). The existence of the Cu3OH fragment is confirmed by a pseudotetrahedral oxygen environment, by detection of the OH hydrogen atom, and by stoichiometry. In the trinuclear unit the metal ions show, in the first approximation, a pseudo-square-planar pyramidal environment forming a CuN2O3 chromophore; three of the basal positions are occupied by N,N,O aat ligand atoms, the fourth one is occupied by the oxygen of the central OH group, and the apical site is occupied by an oxygen atom from a water molecule in the case of two of the copper(II) atoms and by an oxygen atom from the coordinating anion in the case of the third metal ion. The three compounds exhibit strong antiferromagnetic interaction, with similar J constants [J = -197.7 (1), J = -190.9 (2), J = -198.2 (3) cm-1], reaching complete spin coupling at ca. 75 K (1)/55 K (2)/95 K (3). At very low temperature the magnetic moment (magnetic susceptibility) falls below that expected for one unpaired electron. Magnetic parameters are discussed on the basis of the structural results and compared with those reported in the literature for related trimeric Cu(II) compounds with N-O or N-N peripheral bridges. Solid state EPR spectra of the three complexes recorded at liquid N temperature show axial signals. Crystal data: C14H20Cu3F6N12O12S2 (1) (Mw = 917.16) crystallizes in the monoclinic space group, P2(1)/c, Z = 4, with cell dimensions a = 13.080(2) A, b = 17.202(2) A, c = 13.840(2) A, beta = 92.40(1) degrees, and V = 3111.3(7) A3, Dcalcd = 1.958 Mg m-3; the final agreement values were R1 = 0.0582 and wR2 = 0.1462 for 7107 unique reflections. C12H24Cu3N14O14 (2) (Mw = 779.07) crystallizes in the triclinic space group, P1, Z = 2, with cell dimensions a = 9.647(2) A, b = 9.985(2) A, c = 15.314(2) A, alpha = 84.080(10), beta = 87.694(10), gamma = 65.030(10) degrees, and V = 1330.1(4) A3, Dcalcd = 1.945 Mg m-3; the final agreement values were R1 = 0.0397 and wR2 = 0.0950 for 7728 unique reflections. C12H20Cl2Cu3N12O14 (3) (Mw = 817.92) crystallizes in the monoclinic space group, P2(1)/a, Z = 4, with cell dimensions a = 14.238(5) A, b = 16.387(6) A, c = 11.678(4) A, gamma = 90.45(2) degrees, and V = 2724.6(18) A3, Dcalcd = 1.994 Mg m-3; the final agreement values were R1 = 0.0616 and wR2 = 0.1279 for 4038 unique reflections.

The synthesis, characterization, and electrochemical, photophysical, and photochemical properties of the compounds [Ru(bpy)(2)(L)](2+) (Ru), [Os(bpy)(2)(L)](2+) (Os), [(L)Os(bpy)(2)Cl](+) (OsCl), [Ru(bpy)(2)(L)Ru(bpy)(2)Cl](3+) (RuRuCl), [Os(bpy)(2)(L)Os(bpy)(2)Cl](3+) (OsOsCl), [Ru(bpy)(2)(L)Os(bpy)(2)Cl](3+) (RuOsCl), and [Os(bpy)(2)(L)Ru(bpy)(2)Cl](3+) (OsRuCl) are reported (bpy = 2,2'-bipyridine, L = 1-methyl-3-(pyrazin-2-yl)-1,2,4-triazole). The Os(bpy)(2) and the Ru(bpy)(2) moieties are coordinated to the pyrazyltriazole ligand in two different ways, i.e. in a bidentate fashion via the triazole ring and N1 of the pyrazine ring and in a monodentate fashion only via N4 of the pyrazine ring. In the homonuclear dimers the monodentate bound metal has an oxidation potential that is approximately 400 mV lower than that of the bidentate bound metal. Spectroelectrochemical investigations suggest the presence of a weak interaction between the metal centers in the dinuclear species. The emission properties of the compounds are indicative of efficient energy transfer in the excited state, leading to emission from only one metal unit. In acetone both RuRuCl and the OsRuCl show photodissociation of the monodentate ruthenium moiety; however, RuOsCl and OsOsCl were found to be photostable.

Two new iron(II) compounds with the formula [Fe(3)(iptrz)(6)(H(2)O)(6)]X(6).xH(2)O (with iptrz = 4-isopropyl-1,2,4-triazole and X = p-toluenesulfonate (Tos) or trifluoromethanesulfonate (Trifl)) were synthesized. The crystal structure of [Fe(3)(iptrz)(6)(H(2)O)(6)](Tos)(6).2H(2)O (I) has been solved at room temperature. Crystals of I are triclinic, space group P&onemacr; with a = 12.8820(11) Å, b = 15.580(2) Å, c = 24.445(4) Å, alpha = 79.270(12) degrees, beta = 86.688(11) degrees, gamma = 83.007(8) degrees, Z = 2. The structure of I consists of linear trinuclear cations with a +6 charge and noncoordinated anions and lattice water molecules. The central iron ion is located on an inversion center and is coordinated by 6 nitrogen atoms of 6 iptrz molecules bridging via the nitrogen atoms in the 1,2-positions. Each external iron atom completes its coordination sphere with three coordinated water molecules. The temperature dependent magnetic measurements of compound I and [Fe(3)(iptrz)(6)(H(2)O)(6)](Trifl)(6) (II) show that both compounds exhibit a gradual spin conversion of the central iron ion centered at T(1/2) = 242 K for I and 187 K for II. Temperature dependent Mössbauer spectroscopy measurements on I show the behavior expected for a compound of this nature. The measurements on II indicate a strong influence of the spin conversion of the central iron ion on both external iron ions. The nature of this phenomenon is proposed to be connected to a very rigid lattice structure (ionic, H-bonding) connecting the trinuclear units.