A new facile synthesis of chelate reagent via 2-aminomethylpyridine-Co(III) complex: 2,3,5,6-tetra(2-pyridyl)pyrazine

2-Aminomethylpyridine $\text{(1)}$ readily reacted with Co(II) ion to give a chelate complex which reacted with oxygen to form, presumably, a μ-peroxodicobalt(III) complex or a Co(III)-$\text{(1)}$ complex, and finally it was transformed to 2,3,5,6-tetra(2-pyridyl) pyrazine.     

Copper(II) and lead(II) complexes based on 2,3,5,6-tetrakis(2-pyridyl)pyrazine as a polydentate ligand

The Cu(II) complexes [Cu(Tppz)(Dipic)] · 8H₂O (I) and [Pb₂(Tppz)Cl₄] _n (II), where Tppz, H2Dipic are 2,3,5,6-tetrakis(2-pyridyl)pyrazine, dipicolinic acid, respectively, have been synthesized and characterized by elemental analyses, IR, cyclic voltammetry, and electronic spectral studies. Solid state structures of both complexes have been determined by single crystal X-ray crystallography. An ORTEP drawing of two complexes shows that the coordination geometry around the metal center is a distorted octahedron. There are extensive conventional intermolecular O-H…O, N-H…O, and weaker C-H…O and C-H…Cl non-classical hydrogen bonds, which cause the stability of the crystal structure. Crystal data for I: monoclinic, space group: C2/c, a = 35.421(3), b = 8.422(6), c = 22.824(8) Å, β = 101.69(2)°, V = 6668(5) ų, Z = 8. Crystal data for II: triclinic, space group P \(\bar 1\) , a = 7.9534(4), b = 8.8682(5), c = 9.4245(5) Å, β = 95.086(2)°, V = 655.93(6) ų, Z = 2.     

Crystal structures and magnetic properties of 2,3,5,6-tetrakis(2-pyridyl)pyrazine (tppz)-containing copper(II) complexes

Four new copper(II) complexes of formula [Cu(2)(tppz)(dca)(3)(H(2)O)].dca.3H(2)O (1), [Cu(5)(tppz)(N(3))(10)](n)() (2), [[Cu(2)(tppz)(N(3))(2)][Cu(2)(N(3))(6)]](n)() (3), and [Cu(tppz)(N(3))(2)].0.33H(2)O (4) [tppz = 2,3,5,6-tetrakis(2-pyridyl)pyrazine and dca = dicyanamide anion] have been synthesized and structurally characterized by X-ray diffraction methods. The structure of complex 1 is made up of dinuclear tppz-bridged [Cu(2)(tppz)(dca)(3)(H(2)O)](+) cations, uncoordinated dca anions, and crystallization water molecules. The copper-copper separation across bis-terdentate tppz is 6.5318(11) A. Complex 2 is a sheetlike polymer whose asymmetric unit contains five crystallographically independent copper(II) ions. These units are building blocks in double chains in which the central part consists of a zigzag string of copper atoms bridged by double end-on azido bridges, and the outer parts are formed by dinuclear tppz-bridged entities which are bound to the central part through single end-on azido bridges. The chains are furthermore connected through weak, double out-of-plane end-on azido bridges, yielding a sheet structure. The intrachain copper-copper separations in 2 are 6.5610(6) A across bis-terdentate tppz, 3.7174(5) and 3.8477(5) A across single end-on azido bridges, and from 3.0955(5) to 3.2047(7) A across double end-on azido bridges. The double dca bridge linking the chains into sheets yields a copper-copper separation of 3.5984(7) A. The structure of 3 consists of centrosymmetric [Cu(2)(tppz)(N(3))(2)](2+) and [Cu(2)(N(3))(6)](2)(-) units which are linked through axial Cu.N(azido) (single end-on and double end-to-end coordination modes) type interactions to afford a neutral two-dimensional network. The copper-copper separations within the cation and anion are is 6.5579(5) A (across the bis-terdentate tppz ligand) and 3.1034(6) A (across the double end-on azido bridges), whereas those between the units are 3.6652(4) A (through the single end-on azido group) and 5.3508(4) A (through the double end-to-end azido bridges). The structure of complex 4 is built of neutral [Cu(tppz)(N(3))(2)] mononuclear units and uncoordinated water molecules. The mononuclear units are grouped by pairs to give a rather short copper-copper separation of 3.9031(15) A. The magnetic properties of 1-4 have been investigated in the temperature range 1.9-300 K. The magnetic behavior of complexes 1 and 4 is that of antiferromagnetically coupled copper(II) dimers with J = -43.7 (1) and -2.1 cm(-)(1) (4) (the Hamiltonian being H = -JS(A).S(B)). An overall ferromagnetic behavior is observed for complexes 2 and 3. Despite the structural complexity of 2, its magnetic properties correspond to those of magnetically isolated tppz-bridged dinuclear copper(II) units with an intermediate antiferromagnetic coupling (J = -37.5 cm(-)(1)) plus a ferromagnetic chain of hexanuclear double azido-bridged copper(II) units (the values of the magnetic coupling within and between the hexameric units being +61.1 and +0.0062 cm(-)(1), respectively). Finally, the magnetic properties of 3 were successfully analyzed through a model of a copper(II) chain with regular alternating of three ferromagnetic interactions, J(1) = +69.4 (across the double end-on azido bridges in the equatorial plane), J(2) = +11.2 (through the tppz bridge), and J(3) = +3.4 cm(-)(1) (across the single end-on azido bridge).     

An OFF-OFF-ON fluorescence sensor for metal ions in stepwise complex formation of 2,3,5,6-tetrakis(2-pyridyl)pyrazine with metal ions

The fluorescence intensity of 2,3,5,6-tetrakis(2-pyridyl)pyrazine (TPPZ) begins to increase at concentrations of metal ions (Mn+) above the 1:2 ratio of metal ion concentration to the initial concentration of TPPZ ([Mn+]/[TPPZ]0 > 0.5), when a 2:1 complex of TPPZ with Mn+ [(TPPZ)2-Mn+] is converted to a 1:1 complex of TPPZ with Mn+ (TPPZ-Mn+), which exhibits strong fluorescence.     

Rhodium(III) and cadmium(II) complexes based on the polypyridyl ligand 2,3,5,6-tetrakis(2-pyridyl)pyrazine (tppz)

Tppz (2,3,5,6-tetrakis(2-pyridyl)pyrazine) complexes [Rh(tppz)(bpy)Cl][PF₆]₂.acetylacetone (bpy = 2,2′-bipyridine) and [{CdCl₂}₂(μ-tppz)].ethylene glycol have been synthesized and characterized by elemental analyses, IR, ¹H NMR, cyclic voltammetry, photoluminescence and electronic spectral studies. Solid state structures of both complexes have been determined by single-crystal X-ray crystallography. The structural determination shows that the dinuclear Cd(II) complex, [{CdCl₂}₂(μ-tppz)], is a 1D coordination polymer. An ORTEP drawing of [Rh(tppz)(bpy)Cl][PF₆]₂.acetylacetone shows that the coordination geometry around the Rh(III) center is a distorted octahedron. [{CdCl₂}₂(μ-tppz)] displays intraligand ¹(π–π^*) fluorescence and can potentially serve as a photoactive material. For the mononuclear Rh(III) complex, only a two-electron reduction process occurs at the metal with the elimination of Cl⁻ ligand. The emission of this complex is assigned as πd^* phosphorescence.     

Synthesis and study of the spectroscopic and redox properties of Ru(II),Pt(II) mixed-metal complexes bridged by 2,3,5,6-tetrakis(2-pyridyl)pyrazine

The mixed-metal supramolecular complexes [(tpy)Ru(tppz)PtCl](PF6)3 and [ClPt(tppz)Ru(tppz)PtCl](PF6)4 (tpy = 2,2':6',2'-terpyridine and tppz = 2,3,5,6-tetrakis(2-pyridyl)pyrazine) were synthesized and characterized. These complexes contain ruthenium bridged by tppz to platinum centers to form stereochemically defined linear assemblies. X-ray crystallographic determinations of the two complexes confirm the identity of the metal complexes and reveal intermolecular interactions of the Pt sites in the solid state for [(tpy)Ru(tppz)PtCl](PF6)3 with a Pt...Pt distance of 3.3218(5) A. The (1)H NMR spectra show the expected splitting patterns characteristic of stereochemically defined mixed-metal systems and are assigned with the use of (1)H-(1)H COSY and NOESY. Electronic absorption spectroscopy displays intense ligand-based pi --> pi* transitions in the UV and MLCT transitions in the visible. Electrochemically [(tpy)Ru(tppz)PtCl](PF6)3 and [ClPt(tppz)Ru(tppz)PtCl](PF6)4 display reversible Ru (II/III) couples at 1.63 and 1.83 V versus Ag/AgCl, respectively. The complexes display very low potential tppz (0/-) and tppz(-/2-) couples, relative to their monometallic synthons, [(tpy)Ru(tppz)](PF6)2 and [Ru(tppz)2](PF6)2, consistent with the bridging coordination of the tppz ligand. The Ru(dpi) --> tppz(pi*) MLCT transitions are also red-shifted relative to the monometallic synthons occurring in the visible centered at 530 and 538 nm in CH3CN for [(tpy)Ru(tppz)PtCl](PF6)3 and [ClPt(tppz)Ru(tppz)PtCl](PF6)4, respectively. The complex [(tpy)Ru(tppz)PtCl](PF6)3 displays a barely detectable emission from the Ru(dpi) --> tppz(pi*) (3)MLCT in CH 3CN solution at RT. In contrast, [ClPt(tppz)Ru(tppz)PtCl](PF6)4 displays an intense emission from the Ru(dpi) --> tppz(pi*) (3)MLCT state at RT with lambda max(em) = 754 nm and tau = 80 ns.     

Building Block Approach to the Construction of Long-Lived Osmium(II) and Ruthenium(II) Multimetallic Complexes Incorporating the Tridentate Bridging Ligand 2,3,5,6-Tetrakis(2-pyridyl)pyrazine

Two classes of synthetically useful bimetallic complexes of the form [(tpy)M(tpp)RuCl(3)](PF(6)) and [(tpy)M(tpp)Ru(tpp)](PF(6))(4) have been prepared and their spectroscopic and electrochemical properties investigated (tpy = 2,2':6',2"-terpyridine, tpp = 2,3,5,6-tetrakis(2-pyridyl)pyrazine, and M = Ru(II) or Os(II)). Synthetic methods have been developed for the stepwise construction of tpp-bridged systems using a building block approach. In all four complexes, the tpp that serves as the bridging ligand is the site of localization of the lowest unoccupied molecular orbital (LUMO). The nature of the HOMO (highest occupied molecular orbital) varies depending upon the components present. In the systems of the type [(tpy)M(tpp)RuCl(3)](PF(6)), the ruthenium metal coordinated to tpp and three chlorides is the easiest to oxidize and is the site of localization of the HOMO. In contrast, for the [(tpy)M(tpp)Ru(tpp)](PF(6))(4) systems, the HOMO is based on the metal, M, that is varied, either Ru or Os. This gives rise to systems which possess a lowest lying excited state that is always a metal-to-ligand charge transfer state involving tpp but can be tuned to involve Os or Ru metal centers in a variety of coordination environments. The synthetic variation of the components within this framework has allowed for understanding the spectroscopic and electrochemical properties. Bimetallic systems incorporating this tpp ligand have long-lived excited states at room temperature (lifetimes of ca. 100 ns). The bimetallic system [(tpy)Ru(tpp)Ru(tpp)](PF(6))(4) has a longer excited state lifetime than the monometallic system from which it was constructed, [(tpy)Ru(tpp)](PF(6))(2). Details of the spectroscopic and electrochemical studies are reported herein.     

Mono-, di- and trinuclear 2,3,5,6-tetrakis(2-pyridyl)pyrazine (tppz)-containing copper(II) complexes: syntheses, crystal structures and magnetic properties

Three new copper(ii) complexes of formula [Cu(tppz)(NCO)(2)].0.4H(2)O (1), [Cu(2)(tppz)Br(4)](2) and [Cu(3)(tppz)(C(5)O(5))(3)(H(2)O)(3)].7H(2)O (3)[tppz = 2,3,5,6-tetrakis(2-pyridyl)pyrazine; C(5)O(5)(2-) = croconate, dianion of 4,5-dihydroxycyclopent-4-ene-1,2,3-trione] have been synthesised and structurally characterized by X-ray diffraction methods. The structure of complex is made up of neutral [Cu(tppz)(NCO)(2)] mononuclear units and uncoordinated water molecules. The mononuclear units are grouped by pairs to give a rather short copper-copper distance of 3.9244(4) angstroms. The structure of complex 1 consists of neutral tppz-bridged [Cu(2)(tppz)Br(4)] dinuclear units, the copper-copper separation across tppz being 6.6198(1) angstroms. The dinuclear units are further connected through weak, double out-of-plane Cu-Br...Cu bridges [Br(1)...Cu(1a) 4.0028(17) angstroms] creating tetranuclear entities, the copper-copper separation through this interaction being 4.3299(21) angstroms. The structure of complex 3 is built of neutral [Cu(3)(tppz)(C(5)O(5))(3)(H(2)O)(3)] trinuclear units and uncoordinated water molecules. Tppz and one of the croconate groups act as bridging ligands, the former exhibiting the bis-terdentate coordination mode and the latter adopting an unusual asymmetrical bis-bidentate bridging mode through three adjacent oxygen atoms. The other two croconate groups exhibit the bidentate coordination mode. The intramolecular copper-copper separations are 6.5417(9)(across tppz) and 4.3234(9) angstroms (through bis-bidentate croconato). The magnetic properties of 2 and 3 have been investigated in the temperature range 1.9-300 K. The magnetic behaviour of complex 2 is that of an antiferromagnetically coupled copper(II) dimer (J = -40.9 cm(-1), the Hamiltonian being H = -JS(A).S(B)). In the case of compound , the chi(M) T vs. T plot is typical of an overall antiferromagnetic coupling with a low-lying spin doublet being fully populated at T < 10 K. The values of the intramolecular antiferromagnetic interactions in 3 are -19.9 (across tppz) and -32.9 cm(-1)(through bridging croconato). Density functional type calculations were performed on model dinuclear fragments of 3 in order to analyze the efficiency of the exchange pathways involved and also to substantiate the coupling parameters.     

Charge delocalization in a cyclometalated bisruthenium complex bridged by a noninnocent 1,2,4,5-tetra(2-pyridyl)benzene ligand

Two ruthenium atoms are covalently connected to the para positions of a phenyl ring in 1,2,4,5-tetra(2-pyridyl)benzene (tpb) to form a linear Ru-tpb-Ru arrangement. This unique structure leads to appealing electronic properties for the biscyclometalated complex [(tpy)Ru(tpb)Ru(tpy)](2+), where tpy is 2,2';6',2″-terpyridine. It could be stepwise oxidized at substantially low potential (+0.12 and +0.55 V vs Ag/AgCl) and with a noticeably large comproportionation constant (1.94 × 10(7)). In addition to the routinely observed metal-to-ligand charge-transfer transitions, [(tpy)Ru(tpb)Ru(tpy)](2+) displays a separate and distinct absorption band at 805 nm with appreciable absorptivity (ε = 9000 M(-1) cm(-1)). This band is assigned to the charge transition from the Ru-tpb-Ru motif to the pyridine rings of tpb with the aide of density functional theory (DFT) and time-dependent DFT calculations. Complex [(tpy)Ru(tpb)Ru(tpy)](2+) was precisely titrated with 1 equiv of cerium ammonium nitrate to produce [(tpy)Ru(tpb)Ru(tpy)](3+), which shows intense multiple NIR transitions. The electronic coupling parameters H(ab) of individual NIR components are determined to be 5812, 4942, 4358, and 3560 cm(-1). DFT and TDDFT calculation were performed on [(tpy)Ru(tpb)Ru(tpy)](3+) to elucidate its electronic structure and spin density population and the nature of the observed NIR transitions. Electron paramagnetic resonance studies of [(tpy)Ru(tpb)Ru(tpy)](3+) exhibit a discernible rhombic signal with the isotropic g factor of ?g? = 2.144. These results point to the strong orbital interaction of tpb with metal centers and that tpb behaves as a redox noninnocent bridging ligand in [(tpy)Ru(tpb)Ru(tpy)](2+). Complex [(tpy)Ru(tpb)Ru(tpy)](3+) is determined to be a Robin-Day class III system with full charge delocalization across the Ru-tpb-Ru motif.     

Near-IR electrochromism in electropolymerized films of a biscyclometalated ruthenium complex bridged by 1,2,4,5-tetra(2-pyridyl)benzene

Reductive electropolymerization of the biscyclometalated ruthenium complex [(vtpy)Ru(tpb)Ru(vtpy)](2+) [vtpy = 4'-vinyl-2,2':6',2″-terpyridine; tpb = 1,2,4,5-tetra(2-pyridyl)benzene] proceeded smoothly on electrode surfaces. Thanks to the strong electron coupling between the ruthenium centers of the individual monomeric units and strong intervalence charge-transfer absorption in the mixed valence state, the produced adherent metallopolymeric films exhibited near-IR electrochromism with tricolor switching, good contrast ratio (40% at 1165 nm), short response time, low-switching voltage, and long memory time.     

Synthesis and Crystal Structure of N-Benzyl-N'-(2-pyridyl)urea and Its Mononuclear Cu(II) Complex

A new ligand of N-benzyl-N'-(2-pyridyl)urea L and its self-assembly product with CuCl2, [Cu(II)LCl2]∞ 1, have been synthesized and structurally characterized by IR, 1H NMR and single-crystal X-ray diffraction analysis. In the structure of L, the urea groups adopt Z,E conformation to form dimers through intermolecular hydrogen bonds; while in complex 1, it assumes Z,Z conformation to fit for the coordination sphere of the Cu(II) ions. The coordinated units are connected through intermolecular N-H…Cl hydrogen bonds to form an extended 2D framework. Finally, a 3D structure is obtained via π-π stacking interactions between pyridyl rings.     

Mixed valence aspects of diruthenium complexes [((L)ClRu)2(mu-tppz)]n+ incorporating 2-(2-pyridyl)azoles (L) as ancillary functions and 2,3,5,6-tetrakis(2-pyridyl)pyrazine (Tppz) as bis-tridentate bridging ligand

Tppz [2,3,5,6-tetrakis(2-pyridyl)pyrazine]-bridged complexes [((L)ClRu)(2)(mu-tppz)]n+ with structurally similar but electronically different ancillary ligands, 2-(2-pyridyl)azoles (L), were synthesized as diruthenium(II) species. Cyclic voltammetry, EPR of paramagnetic states, and UV-vis-NIR spectroelectrochemistry show that the first two reduction processes occur at the tppz bridge and that oxidation involves mainly the metal centers. The mixed valent intermediates from one-electron oxidation exhibit moderate comproportionation constants 10(4) < K(c) < 10(5) but appear to be valence-averaged according to the Hush criterion. Redox potentials, EPR, and UV-vis-NIR results show the effect of increasing donor strength of the ancillary ligands along the sequence L(1) < L(2) < L(4) < L(3), L(1) = 2-(2-pyridyl)benzoxazole, L(2) = 2-(2-pyridyl)benzthiazole, L(3) = 2-(2-pyridyl)benzimidazolate, L(4) = 1-methyl-2-(2-pyridyl)-1H-benzimidazole. Whereas the mixed valent complexes with L(1) and L(2) remain EPR silent at 4 K, the analogues with L(4) and L(3) exhibit typical ruthenium(III) EPR signals, albeit with some noticeable ligand contribution in the case of the L(3)-containing complex. Intervalence charge transfer (IVCT) bands were found in the visible spectrum for the complex with L(3) but in the near-infrared range (at ca. 1500 nm) for the other systems.     

四（2-吡啶基）吡嗪金属配合物的应用研究进展

2,3,5,6-四(2-吡啶基) 吡嗪(tppz)是一类非常具有吸引力的三联吡啶类配体。2,3,5,6-四(2-吡啶基) 吡嗪金属配合物的研究非常重要,在诸多领域如：分子电子、生物化学、磁学、催化和分子传感器等领域具有潜在的应用前景。本文着重对2,3,5,6-四(2-吡啶基) 吡嗪金属配合物近十年应用领域的研究现状进行综述。