Synthesis and structural characterization of an alternating double aquo-bridged and single cyano-bridged polymeric barium–iron complex: {[Ba2(phen)4(H2O)6Fe(CN)6]·Cl·2(phen)·3H2O}n

A new alternating double aquo-bridged and single cyano-bridged polymeric complex {[Ba₂(phen)₄(H₂O)₆Fe(CN)₆]·Cl·2(phen)·3H₂O}_n (1) (phen = 1,10-phenanthroline) has been synthesized and structurally characterized. In the crystal structure the two centrosymmetric [Ba₂(phen)₄(H₂O)₆] units are bridged through two trans CN groups of [Fe(CN)₆]³⁻ ion, which results in the formation of a zig-zag polymeric chain. In each [Ba₂(phen)₄(H₂O)₆] unit, the two Ba centers are joined by double aquo bridges. Both the Ba atoms are 9-coordinated with distorted mono-capped square antiprismatic geometry. An elaborate hydrogen bonding system holds the parallel polymeric chains together.     

Ferromagnetic coupling in a novel dicyanamide-bridged dinuclear gadolinium(III) complex [Gd2(dca)4(OH)2 (NITpPy)4] (NITpPy = 4-pyridyl-nitronyl nitroxide radical)

The novel six-coordinated gadolinium(III) complex of formula [Gd₂(dca)₄(OH)₂(NITpPy)₄] (1) (dca = dicyanamide, NITpPy = 4-pyridyl-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazolyl-oxy-3-oxide) has been prepared and characterized by X-ray crystallography. Compound 1 is a dimer structure made up of double μ_1,5-dca-bridged gadolinium(III) ions and one terminal dca ligand; variable-temperature magnetic susceptibility measurements reveal the occurrence of a significant ferromagnetic interaction directly spin polarization through the NITpPy–Gd(III)–NITpPy pathway with J = 11.56 cm⁻¹.     

Ferromagnetic mixed tribridged dinuclear copper(II) complex [Cu2(OAc)2(OH)(dpa)2]PF6 · H2O (dpa = 2,2′-dipyridylamine): 3D superstructure based on hydrogen bond and π…π interaction

A new dinuclear complex [Cu₂(OAc)₂(OH)(dpa)₂] PF₆ · H₂O (1) is prepared and structurally and magneto-structurally characterized. The monocationic core contains one acetate in familiar bidentate η¹:η¹:μ₂-bridge and another in the rare monoatomic bridge along with one hydroxo intermediary. 1 packs through N–H…O and O–H…O hydrogen bonds and π…π interaction resulting a 3D supramolecular continuum and displays high-energy intraligand ¹(π − π^*) fluorescence and intraligand ³(π − π^*) phosphorescence in glassy solution.     

The structural characterization and hydroformylation activity of the tri-rhodium complex [Rh3(μ2-dppm)2(μ2-CO)3(K-CO)3]BF4

Rh₂(cod)₂(μ₂-dppm)(μ₂-Cl)]BF₄ (1) rearranges under carbon monoxide to give [Rh₃(μ₂-dppm)₂(μ₂-CO)₃(K¹-CO)₃]BF₄ (2). Complex 2 has been structurally characterized by single crystal X-ray crystallography. The hydroformylation activities of 1 and 2 were compared for substrates styrene and 1-hexene and the activity of 2 found to be unexpectedly high.     

Diplatinum(III) [Cl2(μ2-amidinate)4] compound derived from air oxidation of mononuclear cis-[Pt(NH3)2(amidine-κ)2] complex

The dinuclear platinum(III) complex [Pt₂Cl₂{μ₂-N(H)C(Et)N(H)}₄] (2) has been prepared by heating cis-[Pt(NH₃)₂{NHC(NH₂)Et}₂](Cl)₂ (cis-1) under aeration conditions in an EtOH/H₂O mixture at 70 °C for 2 d and it was characterized by elemental analyses (C, H, N), ESI⁺-MS, IR, ¹H and ¹³C NMR spectroscopies and also by X-ray diffraction. Complex 2 represents the second Pt^III dimer stabilized by the amidinate ligand ever known and it has a lantern-type structure with four amidinate ligands bridging two Pt^III centers with Pt–Pt distance of 2.4809(2) Å.     

Synthesis, structural characterization and third-order non-linear optical property of new three-dimensional metal-organic polymer [Fe2(μ10-btc)0.5(μ2-ox)0.5(μ2-O)1.5]n

One new metal-organic polymer formulated as [Fe₂(μ₁₀-btc)_0.5(μ₂-ox)_0.5(μ₂-O)_1.5]_n 1 (btc = 1,2,4,5-benzenetetracarboxylate, pyramellitate; ox = oxalate) has been synthesized by low-temperature solid-state reaction and characterized by single-crystal X-ray diffraction, elemental analyses, TGA, IR spectra and UV–visible spectra. Complex 1 presents the first 3D coordination network structure constructed by bridging btc, ox and O mixed ligands. In 1, carboxyl groups of btc are all deprotonated and they have a new type of μ₁₀-btc coordination mode. The third-order non-linear optical (NLO) properties of the title compound 1 were also investigated and they exhibit the reverse saturable absorption and self-defocusing performance with modulus of the hyperpolarizability (γ) 5.98 × 10⁻³⁰ esu for 1 in a 7.45 × 10⁻⁴ mol dm⁻³ DMF solution.     

Synthesis of a fluorescent gold(I) complex with a thiosemicarbazone, [Au2(3-NO2-Hbtsc)4]Cl2 · 2CH3CN

Direct reaction of gold(I) chloride with 3-nitrobenzaldehyde thiosemicarbazone (3-NO₂-Hbtsc) in the presence of triphenylphosphine in acetonitrile has yielded ionic complex, [Au₂(3-NO₂-Hbtsc)₄]Cl₂ · 2CH₃CN (1). It exhibited an intense fluorescence band (λ_em) at 383 nm (λ_ex = 300 nm), and two bands of medium intensity at 413 and 436 nm (λ_ex = 350 nm). Complex 1 represents first example of ionic gold(I) complex with a thiosemicarbazone.     

Synthesis, structure and photoluminescence of a novel palladium(I) compound: [Pd3(μ3-Cl)2(dppp)3][Pd2(μ2-Cl)3(PPh3)2](PPh3)2

Pd(PPh₃)₂Cl₂ reacts with PdCl₂ and 1,3-bis(diphenylphosphine)propane (dppp) in ethanol–DMF–pyridine mixed solvent to yield a novel palladium(I) compound [Pd₃(μ₃-Cl)₂(dppp)₃][Pd₂(μ₂-Cl)₃(PPh₃)₂](PPh₃)₂. It features an isolated structure based on [Pd₃(μ₃-Cl)₂(dppp)₃]⁺ cations having triangulo-palladium clusters and [Pd₂(μ₂-Cl)₃(PPh₃)₂]⁻ anions in which the coordination environment of palladium is an unusual tetrahedral geometry. Its photoluminescence is measured.     

Controllable assembly of a 3-D metal–organic supramolecular framework with the inclusion of a well-resolved 1-D water morph

Two mixed-ligand metal–organic complexes [Cd₂(adipato)(phen)₂(NO₃)₂(H₂O)₂](H₂O)₆ (1) and {[Cd(adipato)(phen)](H₂O)₃}_n (2) have been synthesized upon the reaction of Cd(II) nitrate with 1,10-phenanthroline (phen) and adipate under similar conditions. For 1, the adipato-bridged dinuclear entities are extended into a 3-D supramolecular architecture via hydrogen bonds and π–π stacking. Interestingly, a well-resolved 1-D water morphology consisting of alternate cyclic water tetramer and hexamer is detected as the guests in each channel of this 3-D lattice. Whereas 2 represents a layered coordination polymer in which the Cd^II centers are interlinked by adipate dianions via different coordination modes.     

Synthesis and molecular structure of the sodium arsanediyl zincate [(thf)Na]2[(EtZn)6(AsSiiPr3)4]

The reaction of NaAs(H)SiiPr₃ with ZnEt₂ in the presence of additional triisopropylsilylarsane yields the heterobimetallic complex [(thf)Na]₂ [(EtZn)₆(AsSiiPr₃)₄] (1) in the shape of red prisms. The Na–As and Zn–As bond lengths show values of 301/309 pm and between 247 and 260 pm, respectively.     

Preparation and characterization of an unusual tetracobalt-complex; X-ray crystal structure of [Co2(CO)5{μ-P,P(μ-PPh2CCPPh2)}][Co2(CO)4{μ-P-(μ-PPh2CCPPh2)}]

The reaction of bis(diphenylphosphino)acetylene(DPPA) with Co₂(CO)₈ in toluene at 80 °C for 24 h resulted in an alkyne-bridged, diphosphine-chelated tetracobalt-complex, [Co₂(CO)₅{μ-P,P-(μ-PPh₂CCPPh₂)}][Co₂(CO)₄{μ-P-(μ-PPh₂CCPPh₂)}] 3. The X-ray structural studies of 3 reveals that it can be regarded as a dimerized form of two DPPA bridged dicobalt complex, [Co₂(CO)₆(μ-PPh₂CCPPh₂)] 1.     

A hemidirected 1-D coordination polymer [Pb2(H2O)2(HBTC)2] · 3H2O extended in holodirected 3-D by weak Pb–O interactions

A new complex, [Pb₂(H₂O)₂(HBTC)₂] · 3H₂O (H₃BTC = 1,3,5-Benzenetricarboxylic acid) (1), has been synthesized under hydrothermal condition. The single-crystal analysis shows that 1 consists of 1-D double-chains with Pb(II) six-coordinated by three H₃BTC and one H₂O molecule with the Pb–O bond distances in the range of 2.56–2.76 Å. When the Pb–O bonding limit extends from 2.76 to 2.90 Å, the potential weak bonds of Pb–O can be found and the coordination number of Pb will increase from six to nine. As a result, the coordination geometry of Pb(II) transforms from hemidirected to holodirected and an infinite 3-D framework is obtained by the connection of the double-chains. The IR spectrum and the TGA–DTA curve of 1 are also reported in this paper.     

Ionothermal synthesis and characterization of a 3-D (4, 8)-connected porous anionic metal–organic framework entrapped with 1-D [K2(H2O)6] chains

A novel metal–organic coordination polymer, namely, {[K₂(H₂O)₆][Cd₃(1,2,4,5-BTC)₂]}_n (1) (1,2,4,5-BTC = 1,2,4,5-benzenetetracarboxylate), was synthesized in an ionothermal reaction by using an ionic liquid 1-ethyl-3-methylimidazolium bromide ([EMIM]Br) as solvent. Complex 1 features a novel 3-D (4, 8)-connected porous anionic architecture constructed by linking trinuclear Cd subunits with 1,2,4,5-BTC⁴⁻ ligands, which are further filled with 1-D [K₂(H₂O)₆] cationic chains.     

Self-assembled chloro-bridged metallo-prismatic cations of the general formula [M6(η-C5Me5)6(μ3-tpt)2(μ-Cl)6] (M = Rh, Ir; tpt = 2,4,6-tri(pyridin-4-yl)-1,3,5-triazine)

Two cationic pentamethylcyclopentadienyl metal-based hexanuclear complexes with trigonal prismatic architecture have been synthesised through a two-step strategy. The dinuclear complexes [M(η⁵- C₅Me₅)(μ-Cl)Cl]₂ (M = rhodium and iridium) react with 2,4,6-tri(pyridin-4-yl)-1,3,5-triazine (tpt) in dichloromethane to give the trinuclear complexes [Rh₃(η⁵-C₅Me₅)₃(μ₃-tpt)Cl₆] (1) and [Ir₃(η⁵-C₅Me₅)₃(μ₃-tpt)Cl₆] (2), respectively. Addition of silver triflate to 1 and 2 in dichloromethane connects two identical triangular panels to form the hexanuclear metallo-prismatic cations [Rh₆(η⁵-C₅Me₅)₆(μ₃-tpt)₂(μ-Cl)₆]⁶⁺ (3) and [Ir₆(η⁵-C₅Me₅)₆(μ₃-tpt)₂(μ-Cl)₆]⁶⁺ (4), respectively. Cations 3 and 4 have been isolated as their triflate salts and characterised by ¹H NMR, IR and UV/visible spectroscopy.     

Hexanuclear 4d–4f complexes [Ln2Ag4(ina)8(H2O)10][NO3]2 · 4H2O (Ln = Sm, Eu, Dy): Syntheses, structures and photoluminescent properties

Hexanuclear 4d–4f heterometallic complexes, [Ln₂Ag₄(ina)₈(H₂O)₁₀][NO₃] ₂ · 4H₂O [Ln = Sm (1), Eu (2), Dy (3) and Hina = isonicotinic acid], have been synthesized by the hydrothermal reaction of lanthanide oxides, Ag^I, and isonicotinic acid at a suitable temperature. Single-crystal X-ray diffraction studies indicate that these 4d–4f complexes consist of extended 1D zigzag chains structure built upon [Sm₂Ag₄(ina)₈(H₂O)₁₀] subunits connected by Ag–Ag interactions. Furthermore, the photoluminescent properties of the complex 2 were studied.     

An unique stair-like infinite chain polymer containing dimeric N2S3 square-pyramidal iron(III) complex

A one-dimensional stair-like coordination polymer, [Fe₂L₂Na₂(CH₃CN)₂(Et₂O)₂]_n {1, where L⁴⁻ = N,N’-bis-(2-mercaptophenyl)-2-methyl-2-[(2-methylthio)phenylmethyl] malonyl diamide}, was produced from the one-pot reaction of iron(III) chloride with 2-methyl-2-[(2-methylthio)phenylmethyl] malonyl chloride, 2-aminobenzenethiol and sodium hydride in DMF solution, and was structurally characterized. The dimeric pentacoordinate Fe(III) anionic units are linked by two bridging four-coordinate Na⁺ cations. Each trivalent iron atom is equatorially coordinated by two deprotonated carboxamido N and S atoms of the ligand. The bridging S atom, occupying the axial position, accomplishes the square-pyramidal geometry of iron center. The coordination environment is very similar to the unmodified active site of Fe-containing nitrile hydratase. In addition, the electronic and magnetic properties of this dimeric complex are included in this report.     

Synthesis and characterisation of tetraosmium carbonyl clusters bearing an azo type ligand: crystal and molecular structures of [Os4(μ-H)4(CO)11(NC5H4N=NPh)] and [Os4(μ-H)4(CO)10(MeCN)(NC5H4N=NPh)]

Reaction of [Os₄(μ-H)₄(CO)₁₀(MeCN)₂] with one equivalent of 4-phenylazopyridine (4-PAP) in CH₂Cl₂ at ambient conditions afforded two new tetraosmium clusters [Os₄(μ-H)₄(CO)₁₁(NC₅H₄N=NPh)] (1) and [Os₄(μ-H)₄(CO)₁₀(MeCN)(NC₅H₄N=NPh)] (2) in moderate yields. Compound 1 exists as a pair of isomers in solution, which differ in the location of the bridging hydride ligands. The molecular structures of clusters 1 and 2 consist of a highly distorted tetrahedral metal skeleton, with the azo ligand terminally bonded to an osmium atom.     

Ionic liquid as reaction medium for the synthesis and crystallization of a metal-organic framework: (BMIM)2[Cd3(BDC)3Br2] (BMIM = 1-butyl-3-methylimidazolium, BDC = 1,4-benzenedicarboxylate)

An ionic liquid, 1-butyl-3-methylimidazolium bromide, is used as reaction medium for the synthesis and crystallization of a coordination polymer, (BMIM)₂[Cd₃(BDC)₃Br ₂] (1) (BMIM = 1-butyl-3-methylimidazolium, BDC =  1,4-benzenedicarboxylate), which forms an anionic two-dimensional framework with the imidazolium cations located between the layers. This compound is thermally stable up to ca. 340 °C and exhibits blue emission in solid state at room temperature. Other characterizations by IR and UV–visible spectra are also described.     

Synthesis, structural characterization and ethylene polymerization behavior of complex [Ph4P][CrCl3{HB(pz)3}] [HB(pz)3 = hydrotris(1-pyrazolyl)borate]

Reaction of CrCl₃(THF)₃ with K[HB(pz)₃] in THF leads to the formation of the complex K[CrCl₃{HB(pz)₃}] (1). The salt metathesis of complex 1 with [Ph₄P]Br in CH₂Cl₂ yields the complex [Ph₄P][CrCl₃{HB(pz)₃}](2). The structure of complex 2 · CHCl₃ has been determined by single crystal X-ray diffraction. In the anion the metal centre shows a distorted octahedral geometry with the hydrotris(1-pyrazolyl)borate bonded as N,N′,N″-donor tripod ligand and three chloride atoms completing the co-ordination sphere. Complex 2 in the presence of MAO leads to the formation of an active catalyst for the polymerization of ethylene.     

A new type of supramolecular assembly consisting of crown ether complex cation and a polyoxometalate anion: Synthesis and crystal structure of [Na(C20H24O6)(CH3CN)2]2[Mo6O19] · 4CH3CN

A novel supramolecular assembly consisting of sodium-dibenzo-18-crown-6(DB18C6) complex cation [Na(C₂₀H₂₄O₆)(CH₃CN)₂]²⁺ and isopolyanion [Mo₆O₁₉]²⁻ has been demonstrated in the 3D structure of [Na(C₂₀H₂₄O₆)(CH₃CN)₂]₂[Mo₆O₁₉] · 4CH₃CN (1). Weak intermolecular forces (C–HO hydrogen bonds) between isopolyanion and crown ether play a significant role in the construction of supramolecular framework in the crystal structure of 1. Compound 1 has been characterized in the solid state by single crystal X-ray diffraction, IR, CHN analysis, and TGA.