The chemistry of binuclear palladium(II) and platinum(II) complexes

A series of ionic bis(pyrazole)-silver(I) and -gold(I) complexes [ML2][A] (M = Ag, Au; A = BF4−, PF6−, NO3−), prepared by coordination of the mesomorphic L = Hpz2R(n) or non-mesomorphic L = HpzR(n) pyrazole ligands (Hpz2R(n) = 3,5-bis(4-alkyloxyphenyl)pyrazole; HpzR(n) = 3-(4-alkyloxyphenyl)pyrazole), has been studied. The complexes exhibit enantiotropic behaviour, showing smectic A (SmA) mesophases. The choice of the ligands allows the achievement of ‘H’ or ‘U’ molecular shapes, which appear to be responsible for the attainment of liquid crystal mesophases, these not being dependent on the coordinating or non-coordinating nature of the A counteranions. The new complexes are photoluminescent both in the solid state and in solution at room temperature. In addition, the luminescent behaviour of selected compounds as a function of the temperature indicates that the luminescence is maintained in the mesophase.

/pdf/silver-and-gold-luminescent-metallomesogens-based-on-1wqnw6smon.pdf

Silver and gold luminescent metallomesogens based on pyrazole ligands.

Luminescence of neutral and ionic gold(I) complexes containing pyrazole or pyrazolate-type ligands

Ten new silver and gold trimeric complexes of the type [M3(μ-pz′)3] (M=Au, Ag), where pz′ indicate pyrazolato ligands derived from mesogenic 3,5-disubstituted 1H-pyrazoles or non-mesogenic 3-substituted 1H-pyrazoles HpzR (R=C6H4OCnH2n+1), were synthesized and characterized. The gold and silver complexes 7, 8, 10, and 11 containing symmetric pyrazolato ligands as bridging groups (; R=C6H4OCnH2n+1, n=4 () and 8 ()) exhibited a trigonal symmetric structure. The same results were obtained for the related silver derivatives 16–18 with 3-substituted pyrazolato ligands (pzR; R=C6H4OCnH2n+1, n=4 (pzbp), 12 (pzddp), and 18 (pzodp)). By contrast the 3-substituted pyrazolato-gold compounds 13–15 adopted an asymmetric molecular structure related to the position of the substituents on the trinuclear core. The thermal behavior of these complexes was investigated by differential scanning calorimetry and polarized-light microscopy. The mesomorphism of the parent 3,5-disubstituted pyrazoles is avoided in their corresponding trinuclear complexes 7, 8, 10, and 11. However, the metal derivatives 14 and 17 containing the asymmetric 3-[4-(dodecyloxy)phenyl]pyrazolato ligand were found to have liquid-crystal properties. These compounds exhibited monotropic behavior with columnar mesophases that could be related to the disc-like shape of the molecular core and the appropriate length of the alkyloxy chain. For comparative purposes, the X-ray structure of the related gold complex [Au3(μ-)3] (9) having phenoxyphenyl substituents at the 3- and 5-positions of the pyrazolato ligand is also described. The molecular structure is formed by a non-planar (AuNN)3 core, containing three Au-atoms bridged by three pyrazolato ligands. The molecular packing is described as a columnar organization, the shortest Au ⋅⋅⋅Au distance being 4.639(1) A between consecutive trimers.

Silver and Gold Trinuclear Complexes Based on 3‐Substituted or 3,5‐Disubstituted Pyrazolato Ligands. X‐Ray Crystal Structure of cyclo‐Tris{μ‐[3,5‐bis(4‐phenoxyphenyl)‐1H‐pyrazolato‐κN1 : κN2]}trigold Dichloromethane ([Au(μ‐$\rm{ pz^{pp_2 }}$)]3⋅CH2Cl2)

Five-membered ring systems containing two nitrogen atoms adjacent to each other are called pyrazoles. This chapter serves to cover the extensive literature on pyrazoles during the 10 year period, 1996–2006. The previous two chapters of this series, on pyrazoles, dealt more with the theoretical, experimental structural, and thermodynamic methods and less with the reactivity, synthesis, and applications of pyrazoles. During the last 10 years, more literature has appeared on the synthesis and reactivity of pyrazole-fused ring systems. Furthermore, the medicinal chemistry applications of pyrazoles and fused ring systems have found numerous applications in drug discovery. Also, pyrazoles have been utilized as reagents in synthesis. This chapter focuses on these current developments.

4.01 – Pyrazoles

Bridged 3,5-disubstituted pyrazolate ligands as support of metallomesogens containing [Pd(η3-C3H5)]+ fragments: X-ray crystal structure of [Pd(η3-C3H5)(μ-pzR2)]2·CH2Cl2 (R=C6H4OC12H25). Part III

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Bridged 3,5-disubstituted pyrazolate ligands as support of metallomesogens containing [Pd(η3-C3H5)]+ fragments: X-ray crystal structure of [Pd(η3-C3H5)(μ-pzR2)]2·CH2Cl2 (R=C6H4OC12H25). Part III