[Ni（H2O）（tptz）（C2O4）]·4H2O的合成、结构与表征

在CH3OH／H2O混合溶剂中，经2，4，6-三（2-吡啶基）-1，3，5-三嗪（tptz）、草酸和新制Ni（OH）2／NiCO3反应合成得到配合物[Ni（H2O）（tptz）（C2O4）]·4H2O．单晶X-射线衍射分析表明：它与已报道的[M（H2O）（tptz）（C2O4）]·4H2O（M=Co（2）、Cu（3）、Zn（4））配合物同晶形，属三斜晶系，P1空间群，晶胞参数a=7．760（2）A，b=12．116（2）A，c=13．031（3）A，α=78．76（4）°，β=83．84（3）°，γ=78．69（3）°，V=1175．3（5）A^3，Z=2，Dc=1．543，F（000）=562，R1=0．0472，wR2=0．1350，GOF=1．088．在配合物的结构基础上与同晶形结构进行比较分析，并研究了它们的IR及TG／DTA测试表征．     

[Cu2I2(tptz)]n的合成和晶体结构研究

用溶液法以碘化亚铜和tptz反应得到Cu(Ⅰ)的配位聚合物[Cu2I2(tptz)]n(1)(tpzt=2,4,6-tris(pyrazole-1-yl)-1,3,5-s-triazine),对该化合物进行了元素分析,红外光谱,XRD,热重等表征,并测定了它的单晶结构.配位聚合物[Cu2I2(tptz)]n(1)属单斜晶系,C2/c空间群,晶体学数据为:a=1.30683(17)nm,b=1.25425(16)nm,c=1.14732(15)nm,β=94.940(2)°,Z=4.tptz以双联吡啶形的配位方式和Cu(Ⅰ)配位形成一条Z字形的1D链.     

Complexes derived from the general copper(II)/maleamic acid/N,N′,N′′-chelate reaction systems: Synthetic,reactivity, structural and spectroscopic studies

The synthetic investigation of the Cu^II/maleamate(−1) ion (HL⁻)/N,N′,N′′-chelate general reaction system has allowed access to compounds [Cu₂(HL)₂(bppy)₂](ClO₄)₂·H₂O (1·H₂O), [Cu(HL)(bppy)(ClO₄)] (2) and [Cu(HL)(terpy)(H₂O)](ClO₄) (4) (bppy = 2,6-bis(pyrazol-1-yl)pyridine, terpy = 2,2′;6′,2′′-terpyridine). In the absence of externally added hydroxides, compound [Cu₂(L′)₂(bppy)₂](ClO₄)₂ (3) was obtained from MeOH solutions; L′⁻ is the monomethyl maleate(−1) ligand which is formed in situ via the Cu^II-assisted HL⁻ → L′⁻ transformation. In the case of tptz-containing (tptz = 2,4,6-tris(2-pyridyl)-1,3,5-triazine) reaction systems, the Cu^II-assisted hydrolysis of tptz to pyridine-2-carboxamide (L1) afforded complex [Cu(L1)₂(NO₃)₂] (5). The crystal structures of 1–5 are stabilized by intermolecular hydrogen bonding and π–π stacking interactions. Characteristic IR bands of the complexes are discussed in terms of the known structures and the coordination modes of the ligands.     

A 3D Supramolecular Pd（Ⅱ） Complex via Hydrogen-bonding and Weak M…M Interactions

The reaction of 2,4,6-tris（2-pyridyl）-1,3,5-triazine （tptz） and K2PdCl4 in THF/H2O （10：1） results in the hydrolysis of tptz to bis（2-pyridylcarbonyl）amide anion （bpca）, and affords complex Pd（bpca）Cl 1, which is the first example of Pd（Ⅱ）-promoted hydrolysis of ligands. Crystal data for 1： orthorhombic, space group Pbcn, a = 12.0136（17）, b = 14.180（2）, c = 6.9747（11）A, V= 1188.2（3） A3, Z = 4, Mr = 368.06, Dc = 2.058 g/cm3, F（000） = 720,μ = 1.786 mm^-1, λ（MoKα） = 0.71073 A, T= 293（2） K, 2θmax = 54.9°, GOOF = 1.085, the final R= 0.0647 and wR = 0.1051 for 1234 observed reflections with I 〉 2σ（I） （refinement on F2）. Complex 1 is connected through hydrogen bonding to give a 2D network. And weak Pd...Pd interactions are also found between adjacent molecules with the distance of 3.6074（5） A, so the complex is further extended into a 3D supramolecular structure. Thermal gravity analysis （TGA） shows that 1 exhibits high thermal stability below 310℃. X-ray powder diffraction （XRD） and UV/Vis spectrum of 1 are also discussed.     

Reactions of 2,4,6-tripyridyl-1,3,5-s-triazine and its Fe(ii) complex with OH· and eaq-

Summary Pulse radiolysis studies indicated that OH^· and e_aq^- formed adducts with 2,4,6-tripyridyl-1,3,5-s-triazine (tptz). The OH-adduct showed an absorption maximum at 290 nm, while the adduct formed from the attack of e_aq^- and subsequent protonation of the anion, has an absorption maximum at 300 nm. In case of the complex, Fe(tptz)₂²⁺, both OH^· and e_aq^- gave ligand centered adducts. All the adducts decayed by second order dimerization or disproportionation, a disproportionation reaction in case of the complex.     

Synthesis,characterization, crystal structure and oxygen-evolution activity of a manganese(II) complex with 2,4,6-tris (2-pyridyl)-1,3,5-triazine

The title complex [Mn(tptz)(CH₃COO)(OH₂)₂]NO₃ was synthesized through the reaction of tptz (2,4,6-tris(2-pyridyl)-1,3,5-triazine), nitric acid and manganese(II) acetate. The molecular structure was characterized by X-ray diffraction, elemental analysis, electrochemistry, EPR, IR, fluorescence and UV–Vis spectroscopy and its oxygen evolving activity has been studied. X-ray structure analysis shows that each Mn(II) ion is seven coordinated by a bidentate acetate, three nitrogen atoms of tptz and two oxygen atoms from two water ligands, which are coordinated in axial positions. The complex acts as an oxygen evolving complex with oxone (2KHSO₅·KHSO₄·K₂SO₄) as primary oxidant in aqueous solution with a turnover number of 1 (mol of O₂/mol of the complex). Kinetic studies revealed a first-order dependence on the complex and oxidant. The EPR spectrum shows that the mononuclear complex oxidize to a Mn^III,IV₂ di-μ-oxo by oxone.