Organotin Dyes: Synthesis and Structural Characterization of Dibutyltin and Dimethyltin Complexes with 2, 2′‐Dihydroxyazobenzene

The preparation and structures of 2, 2′‐dihydroxyazobenzenato‐dibutyl‐tin [Bu₂SnL] and 2, 2′‐dihydroxyazobenzenato‐dimethyl‐tin [Me₂SnL] are described. The complexes were characterized by IR, NMR (¹H, ¹³C, ¹¹⁹Sn) and UV/VIS spectra. The crystal structures were determined by X‐ray diffraction on single crystals. [Bu₂SnL]: monoclinic, space group P2₁/c, cell constants at 208 K: a = 860.73(5), b = 973, 51(18), c = 2340.0(3) pm, β = 93.615(11)°; R₁ = 0.0546. [Me₂SnL]: orthorhombic, space group Pbcn, cell constants at 208 K: a = 1914.6(4), b = 1041.3(3), c = 1323.27(14) pm; R₁ = 0.0529.     

Iron and Nickel Complexes Containing β‐Diketiminato Ligands with Thioether Tethers

A novel β‐diketiminato ligand precursor, LH ( II ), containing thioether tethers was synthesized by the reaction of acetylacetone and 2‐methylthioaniline. II was deprotonated and used in the synthesis of two iron(II) complexes, [LFeCl] ( 1 ), and [LFeOTf] ( 2 ), and one nickel(II) complex, [LNiBr] ( 3 ). All three compounds were characterized by means of single crystal X‐ray diffraction and their structures are discussed.     

3‐(Arylhydrazono)pentane‐2, 4‐diones and their Complexes with Copper(II) and Nickel(II) — Synthesis and Crystal Structures

A series of new 3‐(arylhydrazono)pentane‐2, 4‐diones ( 1 ‐ 6 ) synthesized from pentane‐2, 4‐dione and diazonium salts of respective anilines using the procedure of Japp‐Klingemann are described. Complexes with Cu^II and Ni^II salts are prepared ( 7 ‐ 10 , respectively). Spectroscopic properties of these compounds have been studied and X‐ray crystal structures of selected hydrazones ( 3 , 4 , 6 ) and of the hydrazone complexes ( 7 ‐ 10 ) are reported. The structures of the uncomplexed hydrazones feature an intramolecular N‐H···O interaction to yield a six‐membered H‐bond ring reflecting preference of the hydrazone tautomeric structure. All the complexes are mononuclear 2:1 (L:M) structures of six‐membered chelate type involving N₂O₂ binding sites that are quadratic arranged but differ in the entire coordination environment dependent on the metal and the ligand substitution including distorted octahedral and quadratic pyramidal coordination geometries in the Cu^II complexes 7 and 8 or nearly regular square planar coordination geometry in the Ni^II complexes 9 and 10 , respectively. In the crystal packings, strong and weak H‐bond interactions cause supramolecular network structures.     

Phenylimido Complexes of Technetium and Rhenium with Maleonitriledithiolate

[Tc(NPh)Cl₃(PPh₃)₂] or [Re(NPh)Cl₃(PPh₃)₂] react with two equivalents of Na₂mnt (mnt^2– = 1,2‐dicyanoethene‐1,2‐dithiolate) with formation of anionic complexes of the composition [M(NPh)(mnt)₂]^–. The products can be isolated as large red blocks of their AsPh₄⁺ salts. The complex anions contain square‐pyramidal coordinated metal atoms with the phenylimido ligands in apical positions. The M–N–C bonds are almost linear. A similar phenylimido complex with an additional amino group was synthesized from [Re(NC₆H₄‐4‐NH₂)Cl₃(PPh₃)₂]. The presence of such substituents may allow coupling of the metal complexes to biomolecules such as peptides, proteins, or sugars, provided the M=N bonds are sufficiently stable against hydrolysis.     

Ein Beitrag zu Rhenium(II)‐, Osmium(II)‐ und Technetium(II)‐Thionitrosylkomplexen vom Typ [M(NS)Cl4py]—: Darstellung,Strukturen und EPR‐Spektren

A Contribution to Rhenium(II)‐, Osmium(II)‐, and Technetium(II)‐Thionitrosyl‐Complexes: Preparation, Structures, and EPR‐Spectra The reaction of [Re^VINCl₄]^— and [Os^VINCl₄]^— with S₂Cl₂ leads to the formation of the thionitrosyl complexes [M^II(NS)Cl₄]^— (M = Re, Os) which could not be isolated as pure compounds. Addition of pyridine to the reaction mixture results in the formation of the stable compounds trans‐(Ph₄P)[Os^II(NS)Cl₄py], trans‐(Hpy)[Os^II(NS)Cl₄py], trans‐(Ph₄P)[Re^II(NS)Cl₄py], and cis‐(Ph₄P)[Re^II(NS)Cl₄py]. The crystal structure analyses show for trans‐(Ph₄P)[Os^II(NS)Cl₄py] (monoclinic, P2₁/n, a = 12.430(3)Å, b = 18.320(4)Å, c = 15.000(3)Å, β = 114.20(3)°, Z = 4), trans‐(Hpy)[Os^II(NS)Cl₄py] (monoclinic, P2₁/n, a = 7.689(1)Å, b = 10.202(2)Å, c = 20.485(5)Å, β = 92.878(4)°, Z = 4), trans‐(Ph₄P)[Re^II(NS)Cl₄py] (triclinic, P1¯, a = 9.331(5)Å, b = 12.068(5)Å, c = 15.411(5)Å, α = 105.25(1)°, β = 90.23(1)°, γ = 91.62(1)°, Z = 2), and cis‐(Ph₄P)[Re^II(NS)Cl₄py] (monoclinic, P2₁/c, a = 10.361(1)Å, b = 16.091(2)Å, c = 17.835(2)Å, β = 90.524(2)°, Z = 4) M‐N‐S angles in the range 168‐175°. This indicates a nearly linear coordination of the NS ligand. The metal atom is octahedrally coordinated in all cases. The rhenium(II) thionitrosyl complexes (5d⁵ “low‐spin” configuration, S = 1/2) are studied by EPR in the temperature range 295 > T > 130 K. In addition to the detection of the complexes formed during the reaction of [Re^VINCl₄]^— with S₂Cl₂ EPR investigations on diamagnetically diluted powders and single crystals of the system (Ph₄P)[Re^II/Os^II(NS)Cl₄py] are reported. The ^{185, 187}Re hyperfine parameters are used to get information about the spin‐density distribution of the unpaired electron in the complexes under study. [Tc^VINCl₄]^— reacts with S₂Cl₂ under formation of [Tc^II(NS)Cl₄]^— which is not stable and decomposes under S₈ elimination and rebuilding of [Tc^VINCl₄]^— as found by EPR monitoring of the reaction.     

Coordination Architectures of Lanthanum Complexes Based on Bifunctional 5‐Substituted Tetrazolecarboxylate Ligands

Three complexes of bifunctional 5‐substituted tetrazolatecarboxylate ligands [2‐(5‐(pyrazin‐2‐yl)‐2H‐tetrazol‐2‐yl)acetic acid (Hpztza), 3‐(5‐amino‐2H‐tetrazol‐1(5H)‐yl)propanoic acid (Hatzp), and N,N′‐bis(tetrazol‐5‐yl)anime‐N2,N2′‐diacetic acid (H₂datza)], namely a mononuclear structure [La(pztza)₂(H₂O)₅] · 4H₂O · pztza ( 1 ), a 1D polymeric chain structure [La₂(atzp)₄(H₂O)₈] · 2NO₃ · 2H₂O ( 2 ), and a 2D layer network [La(datza)(H₂O)₃] · 4H₂O ( 3 ) were prepared and structurally characterized by elemental analysis, IR spectroscopy, and single‐crystal X‐ray diffraction. The structures of these complexes are controlled not only by the number and different coordination modes of the tetrazole‐carboxylate ligands but also the different 5‐substituents of the tetrazole ring. The complexes show ligand‐centered luminescence at room temperature in the solid state. The obvious enhancements in luminescence make these complexes to be the potential materials for optical use.     

Kupferkomplexe des neuen Chelatliganden 1‐Methyl‐2‐(2‐thiophenolato)‐1H‐benzimidazol (mtpb) und dessen Oxidationsprodukten

Copper Complexes of the New Chelate Ligand 1‐Methyl‐2‐(2‐thiophenolato)‐1H‐benzimidazole (mtpb) and of its Oxidation Products Anodic electrolysis of copper in acetonitrile in the presence of Hmtpb leads to formation of yellow [Cu₄(mtbp)₄] which was crystallized as a dichloromethane solvate with two crystallographically independent cluster molecules in the unit cell. The copper(I) atoms exhibit slightly pyramidal S₂N coordination with bridging thiolate sulfur atoms. The two clusters contain the four copper atoms arranged in a more (Cu1‐Cu4) or less (Cu5‐Cu8) distorted bisphenoidal arrangement. Reaction of mtpb^— with Cu(ClO₄)₂ under anoxic conditions also produces [Cu₄(mtpb)₄]. However, the admittance of O₂ in the reaction of mtpb^— with copper(II) acetate in methanol causes oxidation of the sulfur atoms; a square‐pyramidal configurated copper(II) complex [Cu(CH₃CO₂‐κ²O)(L₁‐κN)(L₂‐κN, O)] has been isolated and crystallographically characterized in which L₁ is the neutral sulfinic methyl ester and L₂^— is the sulfonate derived from mtpb^—.     

Complexes of 2, 6‐Bis(hydroxymethyl)pyridine with Different Copper(II) Salts Involving the Anions Chloride,Perchlorate, Nitrate and Acetate. Synthesis and Crystal Structures of the Complexes

Complexes of 2, 6‐bis(hydroxymethyl)pyridine (dhmp) with different Cu^II salts [CuCl₂·6H₂O, Cu(ClO₄)₂·6H₂O, Cu(NO₃)₂·3H₂O, Cu(CH₃COO)₂·H₂O] are prepared ( 1 — 5 , respectively), studied by IR, and their crystal structures reported. Dependent on the anion kind, influences on the distortion of the co‐ordination polyhedron, the distribution of donor sites, the formation of a mono‐ or binuclear complex, and the resultant packing structure of the complex are observed, although in no case the counterions of the used Cu^II salts or water of hydration were found in the co‐ordination sphere. Crystal structures of 1 — 5 indicate hexaco‐ordination of the Cu^II ions with N₂O₄‐environment and show that 1 — 4 are mononuclear 2:1 (L:M) complexes, but 5 is a binuclear 4:2 complex. Crystallization of Cu(ClO₄)₂·6H₂O with dhmp yielded two different complexes ( 2 / 3 ). In 3 , one of the dhmp components is mono‐deprotonated and acts as an anionic ligand. The same behavior is found in 5 . Whereas in the neutral ligand complexes 1 , 2 and 4 the basal planes are occupied by O donors, and N atoms are in the axial positions of the octahedrons, in 3 and 5 the bases are formed by two O and two N donor atoms, and O atoms are in the axes. Moreover, complex 3 shows the N atoms in trans position, but 5 in cis position. The packing of the cationic complex units is typical of strong and weak H bond interactions involving the counterions and hydroxylic or aromatic hydrogen atoms to yield complex network structures.     

Synthesis,Crystal Structures,and Luminescent Properties of Two Complexes based on 5‐tert‐Butylisophthalic Acid and 1, 2‐Bis(4‐pyridyl) Ethane

Abstract. Two coordination polymers, namely, [Zn(bpe)_0.5(Htbip)(tbip)_0.5] · H₂O ( 1 ) and [Cd(bpe)_0.5(tbip)] ( 2 ) [H₂tbip = 5‐tert‐butylisophthalic acid and bpe = 1, 2‐ bis(4‐pyridyl) ethane] were synthesized through hydrothermal reactions. Single‐crystal X‐ray diffraction analysis reveals that complex 1 presents a three‐dimensional (3D) six‐connected uninodal structure with the type of topology of svi‐x/I4/mcm → Ibam, whereas complex 2 holds a 2D 4⁴‐sql layer structure. Moreover, the photoluminescent properties of the complexes at room temperature were investigated.     

New Mixed‐Metal Carbonyl Complexes Containing Bridging 2‐Mercapto‐1‐methylimidazole Ligand

Reaction of [Mn₂(CO)₁₀] with 2‐mercapto‐1‐methylimidazole in the presence of Me₃NO at 25 °C afforded two new dimanganese complexes [Mn₂(CO)₆(μ‐SN₂C₄H₅)₂] ( 1 ) and [Mn₂(CO)₇(μ‐SN₂C₄H₅)₂] ( 2 ). Compound 1 consists of two μ‐SN₂C₄H₅ ligands, each bound through the sulfur atom to two Mn atoms and through the nitrogen atom to one Mn atom forming a four‐membered chelate ring. Compound 2 was found to consist of one μ‐SN₂C₄H₅ ligand in a similar bonding mode to 1 but another μ‐SN₂C₄H₅ ligand coordinates through the sulfur atom to one Mn atom and through the nitrogen atom to another Mn atom. Compound 1 was also obtained as the only product from the reaction of [Mn₂(CO)₈(NCMe)₂] with 2‐mercapto‐1‐methylimidazole. In contrast, a similar reaction of [Re₂(CO)₈(NCMe)₂] with 2‐mercapto‐1‐methylimidazole led to the formation of the di‐, tri‐, and tetranuclear complexes [Re₃(CO)₈(μ‐CO)(μ₃‐SN₂C₄H₅)₂(μ‐H)] ( 3 ), [Re₄(CO)₁₂(μ‐SN₂C₄H₅)₄] ( 4 ), and [Re₂(CO)₆(μ‐SN₂C₄H₅)₂] ( 5 ). Compound 3 provides a unique example of a hydrido trirhenium compound. The reaction of [Cr(CO)₃(NCMe)₃] and [Mo(CO)₃(NCMe)₃] with 1 in refluxing THF afforded the mixed metal complexes [CrMn₂(CO)₈(μ‐CO)₂(μ₃‐SN₂C₄H₅)₂] ( 6 ) and [MoMn₂(CO)₈(μ‐CO)₂(μ₃‐SN₂C₄H₅)₂] ( 7 ), respectively, in which two Mn–M (M = Mo, Cr) bonds were formed. In contrast, a similar treatment of [W(CO)₃(NCMe)₃] with 1 yielded two W‐Mn complexes [Mn₂W(CO)₈(μ‐CO)₂(μ₃‐SN₂C₄H₅)₂] ( 8 ) and [Mn₂W(CO)₇(μ‐CO)₂(SN₂C₄H₅)(μ₃‐SN₂C₄H₅)₂] ( 9 ). Treatment of 1 with [Fe₃(CO)₁₂] at 70‐75 °C afforded the trinuclear mixed‐metal complex [FeMn₂(CO)₈(μ‐CO)(μ₃‐SN₂C₄H₅)₂] ( 10 ) and the diiron side product [Fe₂(CO)₆(μ‐S₂N₂C₄H₅)₂] ( 11 ). Compounds 6 ‐ 10 have a bent open structure of three metal atoms linked by two metal‐metal bonds and all, except 9 and 10 , contain a noncrystallographic two‐fold axis of symmetry. Compound 9 is structurally similar to 8 , but it contains a SN₂C₄H₆ ligand, mono coordinated through the exocyclic sulfur atom to the W atom and a Mn–Mn bond instead of a Mn–W bond. Compound 11 comprises two bridging S₂N₂C₄H₅ ligands, which arise from the coupling of 2‐mercapto‐1‐methylimidazole with sulfur.     

Synthesen und NMR‐Untersuchungen von Salzen mit den neuen Anionen [PtXn(CF3)6‐n]2— (n = 0 ‐ 5, X = F,OH, Cl,CN) und die Kristallstrukturanalyse von K2[(CF3)2F2Pt(μ‐OH)2PtF2(CF3)2]·2H2O

Syntheses and NMR Spectroscopic Ivestigations of Salts containing the Novel Anions [PtX_n(CF₃)_6‐n]^2— (n = 0 ‐ 5, X = F, OH, Cl, CN) and Crystal Structure of K₂[(CF₃)₂F₂Pt(μ‐OH)₂PtF₂(CF₃)₂]·2H₂O The first syntheses of trifluoromethyl‐complexes of platinum through fluorination of cyanoplatinates are reported. The fluorination of tetracyanoplatinates(II), K₂[Pt(CN)₄], and hexacyanoplatinates(IV), K₂[Pt(CN)₆], with ClF in anhydrous HF leads after working up of the products to K₂[(CF₃)₂F₂Pt(μ‐OH)₂PtF₂(CF₃)₂]·2H₂O. The structure of the salt is determined by a X‐ray structure analysis, P2₁/c (Nr. 14), a = 11.391(2), b = 11.565(2), c = 13.391(3)Å, β = 90.32(3)°, Z = 4, R₁ = 0.0326 (I > 2σ(I)). The reaction of [Bu₄N]₂[Pt(CN)₄] with ClF in CH₂Cl₂ generates mainly cis‐[Bu₄N]₂[PtCl₂(CF₃)₄] and fac‐[Bu₄N]₂[PtCl₃(CF₃)₃], but in contrast that of [Bu₄N]₂[Pt(CN)₆] with ClF in CH₂Cl₂ results cis‐[Bu₄N]₂[PtX₂(CF₃)₄], [Bu₄N]₂[PtX(CF₃)₅] (X = F, Cl) and [Bu₄N]₂[Pt(CF₃)₆]. In the products [Bu₄N]₂[PtX_n(CF₃)_6‐n] (X = F, Cl, n = 0—3) it is possibel to exchange the fluoro‐ligands into chloro‐ and cyano‐ligands by treatment with (CH₃)₃SiCl und (CH₃)₃SiCN at 50 °C. With continuing warming the trifluoromethyl‐ligands are exchanged by chloro‐ and cyano‐ligands, while as intermediates CF₂Cl and CF₂CN ligands are formed. The identity of the new trifluoromethyl‐platinates is proved by ¹⁹⁵Pt‐ and ¹⁹F‐NMR‐spectroscopy.     

Syntheses,Crystal Structures and Thermal Behavior of Five New Complexes Containing 2, 4, 6‐Trifluorobenzoate as Ligand

Five new complexes containing 2, 4, 6‐trifluorobenzoateas ligand have been synthesized and structurally characterized, namely Li(C₆F₃H₂COO)(H₂O) (P2₁, Z = 2, 1 ),Cs(C₆F₃H₂COO)(C₆F₃H₂COOH) (P2₁/c, Z = 4, 2 ),Cu(C₆F₃H₂COO)₂(H₂O)₂ (P$\bar{1}$ , Z = 1, 3 ), Cu(C₆F₃H₂COO)₂(MeOH) (P2₁/c. Z = 4, 4 ) and Ag(C₆F₃H₂COO)(H₂O) (C2/c, Z = 8, 5 ). 1 – 3 and 5 are coordination polymers forming strands ( 1 , 3 , 5 ) or corrugated layers ( 2 ). In 1 and 2 the benzoate ligand acts as a bridging ligand, whereas in 3 and 5 the benzoate ligand is not bridging and the molecular units are interconnected by bridging water molecules. In 4 and 5, dimeric Cu₂ and Ag₂ units, respectively, are formed with short M ··· M contacts. The dimeric units in 4 resemble the well‐known paddlewheel structural motif. In 5 these dimeric units are further connected by bridging water molecules, whereas in 4 only very weak F ··· H interactions connect the dimeric units. DTA/TG experiments on 1 , 3 and 4 reveal that in a first step solvent molecules (H₂O, MeOH) are unquestionably released. In 1 – 5 the torsion angles of the carboxylate group with respect to the aromatic ring deviate significantly from zero. These results are in very good agreement with the results of quantum chemical calculations of free 2, 4, 6‐trifluorobenzoic acid and its dimer at the DFT and RI‐MP2 level of theory.     

Molecular and Crystal Structures of Pentafluorophenyl‐platinum(II) Complexes with Bis(diphenylphosphino)methane,Bis(diphenylarsino)methane and 1,2‐Bis(diphenylarsino)ethane

The X‐ray crystal structures of [PtCl₂(dppm)], [Pt(C₆F₅)₂L] (L = dppm (bis(diphenylphosphino)methane), dpam (bis(diphenylarsino)methane), dpae (bis(diphenylarsino)ethane)) and [PtCl(C₆F₅)(dpae)] show the complexes to be monomeric with chelating dipnictido ligands, and not alternatives with bridging ligands. In [Pt(C₆F₅)₂(dpam)₂], there are two unidentate diarsine ligands in a cis‐arrangement.     

Novel Octahedral Bis[2‐(1‐aziridinyl)ethanol‐κ2N,O] Complexes of Cobalt(II)

The synthesis and molecular structure of trans‐{bis[(acetato‐κO)‐(2‐(1‐aziridinyl)ethanol‐κ²N,O)]}cobalt(II) ( 4 ) and cis‐{bis[chlorido‐(2‐(1‐aziridinyl)ethanol‐κ²N,O)]}cobalt(II) ( 5 ) is reported. Both neutral chelate complexes are prepared from the corresponding Co^II salt [CoX₂; X = OAc ( 1 ), Cl ( 2 )] and 2‐(1‐aziridinyl)ethanol (azolH, 3 ) in dry dichloromethane. A third, ionic complex, cis‐{bis[aqua‐(2‐(1‐aziridinyl)ethanol‐κ²N,O)]}cobalt(II) diacetate ( 6 ) is formed from 4 in the presence of water and could be crystallized from aqueous dichloromethane. In all cases, 2‐(1‐aziridinyl)ethanol is coordinating as bidentate chelate ligand by the nitrogen and oxygen atom of the aziridinyl and hydroxy moiety. After purification, the compounds have been fully characterized using IR spectroscopy and FAB⁺‐MS. The single‐crystal X‐ray structure analysis revealed a distorted octahedral geometry for all complexes with either trans ( 4 ) or cis ( 5 , 6 ) configuration.     

Koordination von Rhodium(III), Iridium(III) und Kupfer(II) mit dem potentiell vierzähnigen Akzeptorliganden Bis(1‐methylimidazol‐2‐yl)glyoxal (big)

Coordination of Rhodium(III), Iridium(III), and Copper(II) with the Potentially Tetradentate Acceptor Ligand Bis(1‐methylimidazol‐2‐yl)glyoxal (big) Bis(1‐methylimidazol‐2‐yl)glyoxal (big) which has hitherto not been used in coordination chemistry crystallizes to form two perpendicular 1‐methylimidazol‐2‐yl‐carbonyl molecular halves. Out of the various possibilities for mono‐ and bis‐chelate coordination the N,N′‐alternative with a seven‐membered chelate ring is realized in [Cp*Cl(big)Rh](PF₆) as evident from crystal structure analysis. The iridium analogue reacts under hydration of big and elimination of HCl to form a complex cation [Cp*(bigOH)Ir]⁺ which dimerizes in the crystal through hydrogen bonding and contains one five‐ and one six‐membered chelate ring involving the alcoholate‐O. Cu(ClO₄)₂ and the ligand big yield a complex ion [Cu(big)₂]²⁺ with an ESR spectrum that suggests the coordination of the central metal by four N atoms in an approximately planar setting.     

Substituted 2,2′‐Bis(2‐oxidobenzylideneamino)‐4,4′‐dimethyl‐1,1′‐biphenyl Complexes of Zinc

The condensation reaction of 2,2′‐diamino‐4,4′‐dimethyl‐6,6'‐dibromo‐1,1′‐biphenyl with 2‐hydroxybenzaldehyde as well as 5‐methoxy‐, 4‐methoxy‐, and 3‐methoxy‐2‐hydroxybenzaldehyde yields 2,2′‐bis(salicylideneamino)‐4,4′‐dimethyl‐6,6′‐dibromo‐1,1′‐biphenyl ( 1a ) as well as the 5‐, 4‐, and 3‐methoxy‐substituted derivatives 1b , 1c , and 1d , respectively. Deprotonation of substituted 2,2′‐bis(salicylideneamino)‐4,4′‐dimethyl‐1,1′‐biphenyls with diethylzinc yields the corresponding substituted zinc 2,2′‐bis(2‐oxidobenzylideneamino)‐4,4′‐dimethyl‐1,1′‐biphenyls ( 2 ) or zinc 2,2′‐bis(2‐oxidobenzylideneamino)‐4,4′‐dimethyl‐6,6′‐dibromo‐1,1′‐biphenyls ( 3 ). Recrystallization from a mixture of CH₂Cl₂ and methanol can lead to the formation of methanol adducts. The methanol ligands can either bind as Lewis base to the central zinc atom or as Lewis acid via a weak O–H ··· O hydrogen bridge to a phenoxide moiety. Methanol‐free complexes precipitate as dimers with central Zn₂O₂ rings.     

Syntheses,Crystal Structures,and Properties of Lead(II), ­Zinc(II), and Manganese(II) Complexes Constructed from 2, 3, 5, 6‐Tetraiodo‐1, 4‐benzenedicarboxylic Acid

Three new coordination compounds, [Pb(HBDC‐I₄)₂(DMF)₄]( 1 ) and [M(BDC‐I₄)(MeOH)₂(DMF)₂]_n (M = Zn^II for 2 and Mn^II for ( 3 ) (H₂BDC‐I₄ = 2, 3, 5, 6‐tetraiodo‐1, 4‐benzenedicarboxylic acid), were synthesized and characterized by elemental analysis, IR spectroscopy, thermogravimetric (TG) analysis, and X‐ray single crystal structure analysis. Single‐crystal X‐ray diffraction reveals that 1 crystallizes in the monoclinic space group C2/c and has a discrete mononuclear structure, which is further assembled to form a two‐dimensional (2D) layer through intermolecular O–H ··· O and C–H ··· O hydrogen bonding interactions. The isostructural compounds 2 and 3 crystallize in the space group P2₁/c and have similar one‐dimensional (1D) chain structures that are extended into three‐dimensional (3D) supramolecular networks by interchain C–H ··· π interactions. The Pb^II and Zn^II complexes 1 and 2 display similar emissions at 472 nm in the solid state, which essentially are intraligand transitions.     

N,N′‐Bis(Salicylidene)‐1,2‐Cyclohexanediamine Lanthanide(III) Coordination Polymers: Syntheses,Crystal Structures,and Luminescence Properties

The salen‐type ligand H₂L [H₂L = N,N′‐bis(salicylidene)‐1,2‐cyclohexanediamine] was utilized for the synthesis of two lanthanide(III) coordination polymers [LnH₂L(NO₃)₃MeOH]_n [Ln = Eu ( 1 ) and Ln = Lu ( 2 )]. The single‐crystal X‐ray diffraction analyses of 1 and 2 revealed that they are isomorphous and exhibit one‐dimension neutral structure, in which H₂L effectively functions as a bridging ligand and give rise to a chain‐like polymer. The luminescent properties of polymers in solid state and in solution were investigated and 1 exhibits typical red luminescence of Eu^III ions in solid state and dichloromethane solution and 2 emits the ligand‐centered blue luminescence. The energy transfer mechanisms in these luminescent lanthanide polymers were described through calculation of the lowest triplet level of ligand H₂L.     

[Au(Et2dtc)2][TcNCl4] – Darstellung und Struktur

[Au(Et₂dtc)₂][TcNCl₄] – Synthesis and Structure [Au(Et₂dtc)₂][TcNCl₄] (Et₂dtc^– = N,N‐diethyldithiocarbamate) is formed by the reaction of [Au(CO)Cl] with [TcN(Et₂dtc)₂] in dichloromethane. The solid state structure of the compound is characterized by a large triclinic unit cell (space group, P1, a = 9.422(2), b = 22.594(5), c = 32.153(7) Å, α = 72.64(1), β = 85.19(1), γ = 86.15(1)°, Z = 12) and shows an unusual arrangement due to long‐range contacts between the technetium atoms and sulfur atoms of the [Au(Et₂dtc)₂]⁺ units (3.45–3.56 Å) which assemble two anions and one cation to {[TcNCl₄][Au(Et₂dtc)₂] · [TcNCl₄]}^– moieties.     

Palladium(II) Complexes with the Mixed‐Donor Ligand CH3S‐(CH2)3‐PPh2 Crystal Structures of [PdCl2{CH3S‐(CH2)3‐PPh2}n](n = 1, 2)

The phosphorus‐sulfur ligand 1‐(methylthio)‐3‐(diphenylphosphino)‐propane (S‐P3) has been synthesized and characterized by ¹H NMR and ¹³C NMR. Reactions of S‐P3 with [PdCl₂(PhCN)₂] afforded the complexes [PdCl₂(S‐P3)] ( I ) and [PdCl₂(S‐P3)₂] ( II ), in which S‐P3 acts as a bidentate and monodentate ligand, respectively. Compound I crystallizes in monoclinic space group P2₁/n (No. 14) with cell dimensions: a = 8.589(3), b = 15.051(3), c = 17.100(3)Å, β = 102.91(2)°, V = 2154.7(9)ų, Z = 4. Likewise, compound II crystallizes in monoclinic space group P2₁/n (No. 14) with a = 9.993(5), b = 8.613(4), c = 18.721(5)Å, β = 90.18(3)°, V = 1611.3(12)ų, Z = 2. Compound II has a trans square planar configuration with only the P‐site of the ligand bonded to the palladium atom.