Tren Molecule Research Articles

Atmospheric Carbon Dioxide Capture as Carbonate into a Luminescent Trinuclear Cd(II) Complex with Tris(2-aminoethyl)amine Tripodal Ligand

Spontaneous atmospheric CO2 capture as carbonate anion occurred in the synthesis of a trinuclear Cd(II) complex with tris(2-aminoethyl)amine ligand. In reaction two types of compounds were obtained and structurally characterized by X-ray diffraction on a single crystal: initially [{Cd(tren)}3(tren)](ClO4)6·2H2O (1) and subsequently [{Cd(tren)}3(tren)][{Cd(tren)}3(µ3-ηCO3)](ClO4)10 (2). The carbonate anion replaces partially the bridging tren molecule and coordinates in a µ3 fashion. The luminescent properties of the compounds were investigated.

Applying Ni(II) Amine Complexes and Sodium Thiostannate as Educts for the Generation of Thiostannates at Room Temperature

A new versatile and fast room temperature synthesis route was developed in which Na4SnS4·14H2O and selected Ni(II)amine complexes (amine = ethylenediamine (en), 1,2-diaminocyclohexane (1,2-dach), 1,2-diaminopropane (1,2-dap), 2-(aminomethyl)pyridine (2amp)) were reacted in aqueous tren (tren = tris(2-aminoethyl)amine) solutions affording crystallization of six new compounds. During the reaction heteroleptic Ni2+ centered complexes are formed in situ by replacement of two bidentate ligands by the tetradentate tren molecule. The compounds poorer in water of the pseudopolymorphs of [Ni(tren)(en)]2[Sn2S6]·xH2O (x = 2 (1) and 6 (2)) and [Ni(tren)(1,2-dach)]2[Sn2S6]·xH2O (x = 3 (3) and 4 (4)) are formed after a very short reaction time of 1 day. Remarkably, keeping the reaction slurries at room temperature for 7 days the thermodynamically stable water richer compounds were obtained. The remaining compounds, [Ni(tren)(1,2-dap)]2[Sn2S6]·4H2O (5) and [Ni(tren)(2amp)]2[Sn2S6]·10H2O (6), crystallized between 1 and 7...

Expansion of Germanato‐Polyoxovanadate Cluster Cores: Solvothermal Syntheses and Selected Properties of (trenH2)2[{M(tren)}4V15Ge6O48(H2O)] (M = Co and Zn)

Two germanato‐polyoxovanadates with the {V15Ge6O48} cluster core are extended by covalent bonds to four transition metal amine complexes [M(tren)]2+ (M = Co and Zn, tren = tris(2‐aminoethyl)amine). The complexes have bonds to terminal atoms of the Ge2O7 units and such expansion of a germanato‐polyxovanadate was never observed before. The characterization of these compounds revealed the presence of two protonated tren molecules charge balancing the negative charges of the [{M(tren)}4V15Ge6O48(H2O)]4– anion.

Solvothermal synthesis of a new 3-D mixed-metal sulfide framework, (H1.33tren)[In2.67Sb1.33S8]·tren

A new indium(III) antimony(V) sulfide, (H1.33tren)[In2.67Sb1.33S8]·tren, has been prepared solvothermally at 433 K. The compound crystallises in the tetragonal space group I-42d (lattice parameters, a=12.6248(5) and c=19.4387(18)Å at 150K) and contains adamantane-like T2 supertetrahedral units comprised of corner-sharing InS45− and SbS43− tetrahedra. The adamantane-like units are then linked through sulfur vertices to generate an open, 3-D framework structure containing large pores in which neutral, protonated tren (tris(2-aminoethylene)amine) molecules reside. The presence of the organic components was confirmed by solid-state 13C NMR (10kHz), combustion and thermogravimetric analysis. The band gap, obtained from UV–vis diffuse reflectance measurements, is 2.7(2)eV. Stirring with either water or alkali-metal salt solution leads to removal of the neutral tren molecules and an ~9% reduction in unit-cell volume on formation of (H1.33tren)[In2.67Sb1.33S8]·(H2O)4.

Synthesis and characterization of nickel(II) and copper(II) tricyanomethanide complexes with tris(2-aminoethyl)amine as co-ligand

Two new transition metal tricyanomethanide (tcm) complexes with tris(2-aminoethyl)amine (tren) as co-ligand, [Ni(tren)(tcm)2] (1) and [Cu(tren)]3·(μ3-tren)·NO3·5tcm·2H2O (2), were synthesized and characterized by FT-IR spectrum, Thermogravimetry (TG) and single crystal X-ray diffraction analysis. In 1 each nickel(II) atom is coordinated to two tcm anions and one tren molecule to form a mononuclear complex with distorted octahedral geometry. In 2 three copper(II) atoms, each being chelated by a tetradentate tren ligand, are bridged by a μ3-tren ligand to form a cationic trinuclear copper unit. Magnetic susceptibility measurement in the range 2–300K indicates that there are weak ferromagnetic interactions in 1 (θ=1.17K, C=1.17cm3mol−1K, D=3.5cm−1, g=2.17, zJ′=0.44cm−1) and 2 (θ=0.52K, C=1.35cm3mol−1K) respectively.

Chain and layer networks of germanato-polyoxovanadates

Two new members of the {V15E6} (E = As, Sb, Ge, and Si) polyoxovanadate family, [{Mn(tren)(trenH2)}{Mn(tren)}4V15Ge6O48(H2O)0.5]·tren·2H2O (1, tren = tris(2-aminoethyl)amine) and [{Ni(tren)}4(trenH2)2V15Ge6O48(H2O)]·2H2O (2), have been prepared under solvothermal conditions. In 1, the {V15Ge6} cluster is expanded by five in situ formed crystallographically independent Mn2+ complexes via Mn–O(–V/Ge) bonds. Two independent Mn2+ complexes create a rare dinuclear [Mn2O2(tren)2]4+ moiety by bond formation with two terminal O atoms of the Ge2O7 groups of the adjacent {V15Ge6O48(H2O)0.5} clusters, thus connecting the {V15Ge6} cluster shells into a unique charge-neutral helical chain. In the structure of 2, the unusual and hitherto never observed {Ni(tren)(trenH2)Ni(tren)}6+ complex is formed in situ consisting of two tren molecules acting as tetradentate ligands to Ni2+ cations and one additional tren molecule connecting two Ni2+ cations bonded to neighboring cluster anions. The complexes act as linkers joining the {V15Ge6} moieties via Ni–OV bridges, forming a 2D structure. In the coordination polymers of 1 and 2, the spin structure of the {V15Ge6} cluster remains virtually unaffected by the coordinated MnII or NiII spin centers. For both compounds, the magnetic susceptibility can be decomposed into a sum of the contributions of both the {V15Ge6} cluster and the MnII or NiII cations, and a molecular field correction suffices to represent the weak antiferromagnetic coupling between them. Compound 1 is stable up to 350 °C as evidenced by in situ temperature-resolved X-ray powder diffraction studies.

Using a Ni2+ complex as a structure-directing molecule: solvothermal synthesis and properties of [Ni(en)(tren)]4Sb14S25 featuring an unprecedented three-dimensional network architecture

The new thioantimonate [Ni(en)(tren)]4Sb14S25 (1) (tren = tris(2-aminoethyl)amine, en = ethylendiamine) was synthesized under solvothermal conditions using the complex [Ni(en)3]Cl2 as a structure-directing molecule in a slurry of Sb, S and tren as solvent. Under these reaction conditions two of the three en ligands in the [Ni(en)3]Cl2 complex are exchanged by one tren molecule. Compound 1 crystallises in the monoclinic space group P21/c with 4 formula units in the unit cell. Four unique Ni2+ complexes are chelated by one tetradentate tren and one bidentate en molecule. The three-dimensional 3∞[Sb14S25]8− anion is constructed by interconnection of [SbS3] and [SbS4] units forming [Sb2S2], [Sb3S3], [Sb14S14] and [Sb20S20] heterorings as the next hierarchical building groups. The two largest rings are condensed to form the three-dimensional thioantimonate(III) anions. Three different types of channels are identified with diameters of about 7 × 9, 9 × 17, and 8 × 9 Å. The Ni2+ complexes occupy the channels and are located above and below the [Sb14S14] and [Sb20S20] heterorings.

Solvothermal Synthesis and Crystal Structure of the Non‐Centrosymmetric Thioantimonate [Ni(tren)2]2[Ni(tren)(en)]2(Sb4S8)2·0.25H2O

AbstractThe new thioantimonate [Ni(tren)2]2[Ni(tren)(en)]2(Sb4S8)2·0.25H2O (tren = tris(2‐aminoethyl)amine; en = ethylenediamine) was obtained under solvothermal conditions. The compound crystallizes in the non‐centrosymmetric space group P1 with a = 9.424(2), b = 13.010(3), c = 18.883(4) Å, α = 102.46(3), β = 96.11(3), γ = 90.92(3), V = 2246.1(8) Å3, Z = 1. Two of the unique Ni2+ cations are octahedrally surrounded by two tridentate acting tren ligands (type 1) and the other two Ni2+ cations are in an octahedral environment of one tetradentate tren molecule and one bidentate en ligand (type 2). The antimony atoms are in a trigonal pyramidal environment of three sulfur atoms. The SbS3 pyramids are corner‐linked to form two individual [Sb4S8]4– chains running parallel to [010]. Along [001] the two different types of Ni2+‐centered complex cations and the thioantimonate chains alternate. The interchain separations between [Sb4S8]4– chains depend on the space requirements of the two different types of complex cations. Extended N–H···S hydrogen bonding interactions between the complex cations and the anionic chains generates a three‐dimensional network.

Binding and recognition of AMP, ADP, ATP and related inorganic phosphate anions by a tren-based ligand containing a pyrimidine functionality

The interaction of AMP, ADP, ATP and related phosphate, diphosphate and triphosphate anions with the positively charged forms of the HL ligand, constituted by a tren molecule functionalized with a pyrimidine residue, was studied by potentiometric titrations, affording the stability constants of the formed anion complexes, 31P and 1H NMR spectroscopy in aqueous solutions and modelling calculations. The equilibrium data show that electrostatic forces make an important, but not decisive contribution, to the stability of the anion complexes. For nucleotides, 1H NMR spectra showed that the formation of π-stacking interactions between nucleotide adenine and ligand pyrimidine moieties contribute to the stability of these complexes, being very important for those complexes of higher stability. The synergistic action of the different binding groups of the polyfunctional HL receptor leads to a marked recognition of ADP over ATP with a selectivity coefficient as high as 116 at pH 3.3, which is unprecedented in the context of synthetic receptor in water. According to modelling calculations, such exceptional binding selectivity has a strong relation with the increase of stability experienced by ADP complexes upon ADP protonation. A similar phenomenon is observed for HAMP− whose interaction with H3L2+ is at least as strong as that of the more charged HATP3− anion, which is another rare occurrence.

Solvothermal Synthesis of [C6H17N3]Sb10S16: A New Thioantimonate(III) with an in-situ Formed Organic Amine Cation

Abstract The new thioantimonate(III) [C6H17N3][Sb10S16] (C6H17N3 = 2-piperazine-N-ethylamine cation) was obtained under solvothermal conditions showing a unique anionic framework. The compound crystallizes in the monoclinic space group P21/c with four formula units in the unit cell. The lattice parameters are a=11.530(2), b=25.042(5), c = 13.709(3)Å, β =111.25(3)◦,V = 3689(2) Å3. The thioantimonate(III) anion is formed by interconnection of nine trigonal pyramidal SbS3 units and one SbS4 moiety. These primary building units share common corners and edges yielding Sb3S3 and Sb2S2 hetero-rings. Further condensation leads to strong undulated two atoms thick layers extending in the [010] direction, with a modulation period of about 14 Å. Very large Sb31S31 rings within the layers show a ‘double-ellipsoidal’ shape with approximate dimensions of 8.9 ・ 9.3 Å. The cations are located at the inflexion points of the layers and act as pillars between successive layers. The layers are stacked onto each other in a way that channels parallel to [001] are formed accommodating the organic cations. A remarkable observation is that the 2-piperazine-N-ethylamine cation is formed by cyclization of tren molecules (tren = tris(2-aminoethyl)amine) under in-situ conditions.

Solvothermal Synthesis and Crystal Structures of Two Thioantimonate(V) Compounds with the [SbS4]3— Anion Acting as a Monodentate Ligand: [Mn(C6H18N4)(C6H19N4)]SbS4 and [Mn(C6H14N2)3]2[Mn(C6H14N2)2(SbS4)2]·6H2O

AbstractThe two novel thioantimonate(V) compounds [Mn(C6H18N4)(C6H19N4)]SbS4 (I) and [Mn(C6H14N2)3][Mn(C6H14N2)2(SbS4)2]·6H2O (II) were synthesized under solvothermal conditions by reacting elemental Mn, Sb and S in the stoichiometric ratio in 5 ml tris(2‐aminoethyl)amine (tren) at 140 °C or chxn (trans‐1, 2‐diaminocyclohexane, aqueous solution 50 %) at 130 °C. Compound I crystallises in the triclinic space group P1¯, a = 9.578(2), b = 11.541(2), c = 12.297(2)Å, α = 62.55(1), β = 85.75(1), γ = 89.44(1)°, V = 1202.6(4)Å3, Z = 2, and II in the monoclinic space group C2/c, a = 32.611(2), b = 13.680(1), c = 19.997(1)Å, β = 117.237(5)°, V = 7931.7(8)Å3, Z = 4. In I the Mn2+ cation is surrounded by one tetradentate tren molecule, one protonated tren acting as a monodentate ligand and a monodentate [SbS4]3— anion yielding a distorted octahedral environment. In II one unique Mn2+ ion is in an octahedral environment of three bidentate chxn molecules and the second independent Mn2+ ion is coordinated by two chxn ligands and two monodentate [SbS4]3— units leading to a distorted octahedral surrounding. The compounds were investigated and characterized with thermal and spectroscopic methods.

The new thioantimonate(V) (C3H10N)[NiSbS4(C6H18N4)

Turquoise crystals of the title salt, propylammonium di-mu-thio-1:2 kappa(4)S-dithio-2 kappa(2)S-tris(2-aminoethyl)amine-1 kappa(4)N-antimony(V)nickel(II), (C(3)H(10)N)[NiSbS(4)(C(6)H(18)N(4))] or [PAH][Ni(tren)SbS(4)] [where tren is tris(2-aminoethyl)amine and PA is propylamine], were synthesized under solvothermal conditions by reacting [Ni(tren)(2)]Cl(2), Sb and S in a solution of PA. The Ni(II) ion is octahedrally surrounded by four N atoms of the tetradentate tren molecule and by two S atoms of the tetrahedral [Sb(V)S(4)](3-) anion, thus forming the anionic [Ni(tren)SbS(4)](-) part of the compound. Charge balance is achieved through the PAH(+) cation. An extended intermolecular hydrogen-bonding network is observed between the anion and the cation.

Partial substitution of the amine template by alkali metals (Rb, Cs) in the open-framework gallium phosphates ULM-3 and TREN-GaPO

The fluorinated gallium phosphates ULM-3 and TREN-GaPO were hydrothermally synthesized in the presence of organic templates (1,3-diaminopropane, dap, or tris(2-aminoethyl)amine, tren) and alkali metals (Rb, Cs). The solids were structurally characterized by single-crystal X-ray diffraction, and the structure examination indicates that the amine molecules are partially replaced by alkali cations. In ULM-3 (M δ [Ga 3(PO 4) 3(F,OH) 2], (1− δ/2)N 2C 3H 12, (1− δ/2)H 2O; M=Rb, Cs), the alkali metals are located within the 10-ring channels and partially occupy the positions of water and amine molecules ( δ≈0.07 for Rb and δ≈0.18 for Cs). In TREN-GaPO (M 0.5[Ga 3(PO 4) 3(F,OH) 2], 0.5N 4C 6H 21, H 2O; M=Rb, Cs), the alkali cations reside in the 8-ring channels, whereas the tren molecule is trapped within the 12-ring channels. The positions of rubidium and cesium atoms are compared with those of pyridine previously reported for TREN-GaPO.

Hydrothermal synthesis and structural characterization of a new organically templated germanate, Ge(10)O(21)(OH).N(4)C(6)H(21).

A new open-framework germanium oxide Ge(10)O(21)(OH).N(4)C(6)H(21) has been hydrothermally synthesized at 180 degrees C for 6 days by using the tris(2-aminoethyl)amine (tren) molecule as a structure-directing agent. This compound was characterized by means of single-crystal X-ray diffraction and FTIR. It crystallizes in the noncentric monoclinic system Cm (a = 14.0495(2) A, b = 12.8058(3) A, c = 9.2637(2) A, beta = 128.406(1) degrees, Z = 4). Its three-dimensional framework is built up from GeO(4) and GeO(3)(OH) tetrahedra connected by vertexes to GeO(5) trigonal bipyramids and GeO(6) octahedra. A pseudo-cubic building unit ("4-3" subunit) consists of four GeO(4) tetrahedra, two GeO(5) trigonal bipyramids, and one GeO(6) octahedron (Ge(7)). In the "4-3" block, the GeO(5) trigonal bipyramids share a common edge. This Ge(7) entity is linked to three tetrahedral units GeO(3)X (X = O, OH), and this forms an original decameric building unit Ge(10)O(21)(OH) which is new in the germanates crystal chemistry. It results in a relatively dense open framework composed of pear-shape cavities (7(8)6(2)5(2)4(4)3(2)) encapsulating the triprotonated tren molecule. The inorganic network contains small pores delimited by 7-ring channels running along [001].

Two new [Ni(tren)2]2+complexes: [Ni(tren)2]Cl2and [Ni(tren)2]WS4

Both title compounds, bis[tris(2-aminoethyl)amine]nickel(II) dichloride, [Ni(tren)(2)]Cl(2), (I), and bis[tris(2-aminoethyl)amine]nickel(II) tetrathiotungstate, [Ni(tren)(2)]WS(4), (II), contain the [Ni(tren)(2)](2+) cation [tren is tris(2-aminoethyl)amine, C(6)H(18)N(4)]. The tren molecule acts as a tridentate ligand around the central Ni atom, with the remaining primary amine group not bound to the central atom. In (I), Ni(2+) is located on a centre of inversion surrounded by one crystallographically independent tren molecule. In the [Ni(tren)(2)](2+) cation of (II), the Ni atom is bound to two crystallographically independent tren molecules. The Ni atoms in the [Ni(tren)(2)](2+) complexes are in a distorted octahedral environment consisting of six N atoms from the chelating tren molecules. The counter-ions are chloride anions in (I) and the tetrahedral [WS(4)](2-) anion in (II). Hydrogen bonding is observed in both compounds.

Solvothermal synthesis, crystal structure and properties of Mn 2 (tren) 3 [Mo 2 O 2 S 6 ] 2 ·1.3H 2 O exhibiting the new polymeric [Mn 2 (tren) 3 ] n 4+ chain

The novel oxothiomolybdate Mn2(tren)3[Mo2O2S6]2·1.3H2O [tren = tris(2-aminoethyl)amine], synthesized under solvothermal conditions, consists of one-dimensional novel [Mn2(tren)3] n 4+ chains and discrete [Mo2O2S6]2− anions. There are two crystallographically independent chains and four [Mo2O2S6]2− anions in the asymmetric unit. Each Mn atom in the cationic chains is sixfold coordinated by N atoms of the chelating tren molecules. Two of the four crystallographically independent Mn atoms are tridentately coordinated by two tren molecules, whereas the other two are coordinated tetradentately by one tren molecule and monodentately by the remaining primary amino groups from the tren molecules that act as tridentate ligands. The tren ligand bonding modes lead to the formation of the polymeric [Mn2(tren)3] n 4+ chain. One of the four Mn atoms is in the unusual trigonal prismatic coordination state with six surrounding N atoms.

Solvothermal Syntheses, Crystal Structures and Properties of Thiomolybdates with Complex Transition Metal Cations

Abstract The new compounds Ni2(tren)3(MO₂O2S6)2 · 2.75 H2O (I) and CO₂(tren)3(MoS4)2 (II) (tren = tris(2-aminoethyl)amine) were prepared under solvothermal conditions. The structure of I is built up of one-dimensional [Ni2(tren)3]n 4+ chains and isolated [MO₂O2S6]2-anions. Each Ni atom in the cationic chain is surrounded by six N-atoms to form a distorted octahedron. The connection of the Ni-atoms in the [Ni2(tren)3]n 4+ -units with the tren molecules leads to zigzag chains in the (100) plane. The situation is different for compound II which consists of isolated [CO₂(tren)3]4+ cations and discrete tetrahedral [MOS4]2-anions. The Co atom in the cation is in a distorted trigonal bipyramidal environment of four N atoms of one tren molecule and of one N atom from a bridging tren-molecule, building up the dimeric structure of the [CO₂(tren)3]4+ unit. Between the anions and cations of both compounds hydrogen bonding is observed. The thermal behaviour of I and II was investigated using differential thermoanalysis and thermogravimetry. On heating I first looses the crystal water and then decomposes slowly in one step, whereas II decomposes also in one step, but at a significantly lower temperature.