Structure and Spectral Characteristics of 3D-Supramolecular Coordination Polymers Based on Copper Cyanide and Dimethylquinoxaline

The reactions of K₃[Cu(CN)₄], R₃SnCl (R = Me or ph) and 2,3-dimethyl quinoxaline (dmqox) in H₂O/acetonitrile media at room temperature afford the 3D-supramolecular coordination polymers (SCP) ³_￥ [ \textCu ₂ ( \textCN ) ₂ \textdmqox ] ^{ 3}_{\infty } \left[ {{\text{Cu}}_{ 2} \left( {\text{CN}} \right)_{ 2} {\text{dmqox}}} \right] , 1 and ³_￥ [ \textCu ₂ ( \textCN ) ₄ ·( \textPh ₃ \textSn ) ₂ ·\textdmqox ] ^{ 3}_{\infty } \left[ {{\text{Cu}}_{ 2} \left( {\text{CN}} \right)_{ 4} \cdot \left( {{\text{Ph}}_{ 3} {\text{Sn}}} \right)_{ 2} \cdot {\text{dmqox}}} \right] , 2. The structure of the tin free 1 consists of parallel zigzag chains connected by dmqox to form 2D-sheets containing hexagonal 18-atom fused Cu₆(CN)₄(dmqox)₂ rings. The interwoven sheets along the a axis are close packed by extensive H-bonds developing 3D-network structure. The structures of 1 and 2 are investigated by elemental analysis IR, NMR and mass spectra. The ESI⁺ and ESI⁻ mass spectra of 2 support its polymeric nature while the ESI⁺ mass spectrum confirms the expected M. W. suggested by elemental analysis. The ¹³C-NMR spectrum of 2 supports the fact that the network structure of 2 contains the rhombic [Cu₂(μ₃-CN)₂] motif. The structure of 2 was compared with the structure of the reported prototype ³_￥ [ \textCu ₂ ( \textCN ) ₄ ·( \textPh ₃ \textSn ) ₂ ·\textqox ] ^{ 3}_{\infty } \left[ {{\text{Cu}}_{ 2} \left( {\text{CN}} \right)_{ 4} \cdot \left( {{\text{Ph}}_{ 3} {\text{Sn}}} \right)_{ 2} \cdot {\text{qox}}} \right] as well as the other related structures.     

Synthesis,Characterization and Crystal Structure of New Organotin Copper Cyanide Three-Dimensional Supramolecular Coordination Polymer Containing Quinoxaline Molecule

Self assembly of K₃[Cu(CN)₄] with Me₃SnCl and quinoxaline (qox) affords the new organotin ternary adduct _∞³[Cu₂(CN)₃·Me₃Sn·qox], 1, as orange platelet crystals. The supramolecular architecture of 1 consists of [Cu₂(CN)₃]⁻ building blocks connected by the (Me₃Sn)⁺ cations forming infinite corrugated 1D-chains. The chains are bridged by the qox molecules forming 2D-layers containing fused distorted polygons. The layers are interwoven forming 3D-network structure, which are stabilized by close packing effects such as H-bonds as well as Cu···Cu and π–π interactions. IR and mass spectra as well as TGA are investigated.     

Catalytic, Luminescence Activities and Structure of Metal-Organic Frameworks Containing CuCN Building Blocks and Bipodal Bridging Ligands

The reactions of K₃[Cu(CN)₄], R₃SnCl and bipodal ligands, where R = (n-Bu)₃SnCl and L = quinoxaline (qox) and R = Me₃SnCl and L = quinazoline (qaz) afford the red needle crystals of _￥³ [ \textCu₂ ( \textCN )₂ m\text-(qox) ]₂ {}_{\infty }^{3} \left[ {{\text{Cu}}_{2} \left( {\text{CN}} \right)_{2} \mu {\text{-(qox)}}} \right]_{2} , 1 and the orange needle crystals of [Cu₂(CN)₂μ(qaz)]_n, 2. 1 was subjected to single crystals X-ray study while 2 was investigated by IR, ¹H NMR and mass spectra as well as TGA. The crystal structure of 1 exhibits puckered CuCN chains connected by qox molecules forming 2D-sheets. The 2D-sheets contain hexagonal nets stacked in A···A···A fashion. The paralleled sheets are close packed via extensive H-bonds, π–π stacking, strong Cu-Cu interaction and short Cu–C contacts which develop 3D-network. Unique rhombic [Cu₂(μ₃-CN)₂] motifs result as consequence of interwoven of the 2D-sheets. The structure of 2 exhibits different XRPD pattern than that of 1 although, the two structures have the same Cu:CN:L stoichiometric ratio. The emission spectra of 1 and 2 display bands around 390, 420 and 475 nm corresponding to MC transition, ¹(n,π*) → S_o and MLCT, respectively. Thus, 1 and 2 can be considered as examples of room-temperature luminescent Cu-containing polymers which can be used in applications as molecular sensing systems. Also, the oxidative degradation of Metanil Yellow (MY) dye has been investigated by hydrogen peroxide catalyzed by 1 or 2. The catalytic activity of 1 is more pronounced than that of 2.     

New Organotin/CuCN/Quinazoline 3D-Supramolecular Coordination Polymers Having Catalytic and Luminescence Activities

The new bimetallic supramolecular coordination polymers (SCP); ³ _∞[Cu(CN)₂·Me₃Sn·qaz], 1 and ³ _∞[Cu₂(CN)₄·(Ph₃Sn)₂·qaz], 2 (qaz?=?quinazoline), are prepared in water/acetonitrile solvent at room temperature. The structure of 1 consists of the anionic Cu(CN)₂ building blocks connected by the Me₃Sn cations to form zigzag chains which are bridged by qaz creating 2D-sheets. The interwoven infinite sheets are arranged in parallel A···A···A fashion developing 3D-network structure via H-bonds, π–π stacking, and Cu–C contacts. The network structure of 2 exhibits two different copper sites forming two Cu(CN)₂ building blocks which are connected by the Ph₃Sn groups constructing elongated corrugated chains. The qaz ligand connects these chains forming 3D-network structure containing the rhombic [Cu₂(μ₃-CN)₂] motif. 1 and 2 are luminescent materials which can be used in applications as molecular sensing systems. Also, the catalytic activity of 1 and 2 was investigated towards the degradation of Metanil Yellow (MY) dye by dilute solution of hydrogen peroxide as oxidant.     

Structure and Properties of Self-Assembled Ternary Adducts K3[Cu(CN)4], Trimethyl Tin Chloride and 4-Methylpyrimidine

The reaction of K₃[Cu(CN)₄], Me₃SnCl and 4-methylpyrimidine (mpym) at room temperature affords the 3D-octameric _∞ ³ [Cu₈(CN)₈(mpym)₄], I, in water/acetonitrile and the 3D-host–guest _∞ ³ [Cu₈(CN)₈(mpym)₄ dioxane], II. The X-ray single crystal diffraction of I reveals the formation of homometallic octameric building blocks consisting of three fused 11 membered rings. The 3D-network structure of the supramolecular coordination polymer (SCP), I, consists of two crossing sets of parallel corrugated interpenetrating CuCN chains, which are connected by mpym, hydrogen bonds, π–π stacking and cuprophilic interactions. Species II is isostructural with I as indicated by X-ray powder diffraction and spectroscopic measurements.     

One- and Two-Dimensional Cadmium(II) Tetracyanonickelate(II) Coordination Polymers With Imidazole and 2-Methylimidazole Ligands

Two novel cyano-bridged heteropolynuclear complexes, [Cd(im)₄Ni(μ-CN)₂(CN)₂] _n (1) and [Cd(mim)₂Ni(μ-CN)₄] _n (2) (im: imidazole and mim: 2-methylimidazole), have been synthesized and characterized. In 1, the trans-directed cyanide ligands of [Ni(CN)₄]²⁻ anions link two [Cd(im)₄]²⁺ units, whereas in 2, all the cyanide groups take part in bonding with two adjacent [Cd(mim)₂]²⁺ units, resulting 1D and 2D coordination polymers, respectively. The coordination environment of the Cd(II) ion described as distorted octahedral geometry, whereas around the Ni(II) centre had square planar geometry in both complexes. The crystals packing of 1 and 2 were a composite of hydrogen bonding, π···π and C–H···Ni interactions.     

Cooperative effect between iridium and platinum in the carbonylation of methanol to acetic acid

The iodocarbonyl monomer [PtI₂(CO)₂] 7 promotes the iridium catalyzed carbonylation of methanol to acetic acid at low water contents. Studies based on low pressure or high pressure NMR and the use of labeled reactants were conducted close to the real conditions of catalysis in order to get a deeper insight into this system. Carbonylation of CH₃I at low water contents proceeds slowly and the migratory CO insertion step, leading from H[IrI₃(CH₃)(CO)₂] 2-H to H[IrI₃(COCH₃)(CO)₂] 6-H is rate limiting. The dimer [PtI₂(CO)]₂ 7′ reacts immediately with [PPN][IrI₃(CH₃)(CO)₂] 2-PPN (PPN is Ph₃P=N⁺=PPh₃) under nitrogen to afford a mixture of species, among which the key heterobinuclear [Ir–Pt] intermediate [PPN][IrI₂(CH₃)(CO)₂(μ-I)PtI₂(CO)] 8-PPN has been identified; [PPN][IrI₂(CH₃)(CO)₂(μ-I)PtI₂(CO)] 8-PPN can in its turn lead to the formation of [PPN][PtI₃(CO)] 9-PPN, [IrI₂(CH₃)(CO)₂(solv)] 10, [Ir₂I₂(CH₃)₂(μ-I)₂(CO)₄] 3′ and [PPN][Ir₂I₄(CH₃)₂(μ-I)(CO)₄] 11-PPN; all of these species have been characterized. Under CO pressure, [PPN][IrI₂(CH₃)(CO)₂(μ-I)PtI₂(CO)] 8-PPN is a short-lived species that quickly leads to [IrI₂(CH₃)(CO)₃] 4 and [PPN][PtI₃(CO)] 9-PPN showing that the main role of the platinum promoter is to abstract an I⁻ ligand from [PPN][IrI₃(CH₃)(CO)₂] 2-PPN. Under catalytic conditions, I⁻ is abstracted from H[IrI₃(CH₃)(CO)₂] by [PtI₂(CO)₂] 7 and the rate determining step is accelerated; the relevant species H[IrI₃(CH₃)(CO)₂] 2-H, H[IrI₃(COCH₃) (CO)₂] 6-H and H[PtI₃(CO)] 9-H have been observed under 30 bar of CO. A catalytic cycle is proposed, which depicts the cooperative effect between the iridium catalyst and the platinum promoter.     

Cyanide-bridged mixed-valence copper(II/I) coordination polymers: Unique 7-connected sev-type 3D network versus anionic 2D host network encapsulated with cationic complex

Reactions of CuCl₂, K₂[Ni(CN)₄]/K₃[Co(CN)₆], and 5-amino-1H-tetrazole led to cyanide-bridged mixed-valence Cu(II/I) complexes, [Cu(H₂O)₃Cu₃(CN)₅] (1) and [Cu(H₂O)₄][Cu₄(CN)₆] (2).The uncommon semi-closed {Cu₂(CN)₃} dimmers in 1 are bridged by μ₃-C,C,N cyanide ligands to afford rare 1D centipedal-like chain motifs, which are further bridged by μ₂-C,N and metalloligand “CN–Cu(4)–CN” to finish sophisticated zeolite-like 3-D structure. Topologically, 1 is the first example of uninodal 7-connected sev-like cyanide-bridged network. Compound 2 consists of two-dimensional honeycomb-related anionic layers [Cu₄(CN)₆]^2 −, within which the [Cu(H₂O)₄]^2 + cations are intercalated into alternate interlamellar space. Compound 1 shows antiferromagnetic couple arising from pure ground-state configuration of Cu(II) mediated by diamagnetic bridges –CN–Cu^I–CN −. The inclusion compound 2 shows blue photoluminescence originated from Cu(I) center to the unoccupied π* orbital of the cyanide ligand (MLCT) charge transfer.     

Hetero-Metallic Coordination Polymers: Syntheses, Vibrational Spectra, Thermal Analyses and Crystal Structures of trans-[M(N-Meim)2Ni(μ–CN)4] n (M=Cu(II), Zn(II) and Cd(II))

Three cyano bridged hetero-metallic complexes of general formula, trans-[M(N-Meim)₂Ni(μ-CN)₄] _n (N-Meim=N-methylimidazole and M=Cu(II), Zn(II) or Cd(II)) have been synthesized and characterized by vibrational (FT-IR and Raman) spectroscopy, single crystal X-ray diffraction, thermal analyses and elemental analyses. The crystallographic analyses reveal that the complexes, [Cu(N-Meim)₂Ni(μ-CN)₄] _n (1), [Zn(N-Meim)₂Ni(μ-CN)₄] _n (2) and [Cd(N-Meim)₂Ni(μ-CN)₄] _n (3), have polymeric 2D networks. In the complexes, four cyanide groups of [Ni(CN)₄]²⁻ coordinated to the adjacent M(II) ions and distorted octahedral geometries of complexes are completed by two nitrogen atoms of trans N-Meim ligands. Vibration assignments are given for all the observed bands and the spectral features also supported to the crystal structures of polynuclear complexes.     

New host–guest supramolecular coordination polymers based on [(Me3Sn)3Fe(CN)6]n with alkali metal iodides and their applications as electrode materials in batteries

The metal iodides reduce partially the host coordination polymer of the type $ ^{ 3}_{\infty } \left[ {\left( {{\text{Me}}_{ 3} {\text{Sn}}} \right)_{ 3} {\text{Fe}}\left( {\text{CN}} \right)_{ 6} } \right] $ , I, to give new host–guest supramolecular coordination polymers (SCP). The physical and chemical characteristics of the new products were studied by elemental analyses, X-ray powder diffraction, IR, UV/Vis, and solid state NMR spectra. The host–guest SCP are [M_x(Me₃Sn)₃Fe_(1–x)^IIIFe _x ^II (CN)₆]_n M = Li⁺·2H₂O, 1; Li⁺, 2; Na⁺, 3; K⁺, 4; Cu⁺, 5, [Li(Me₃Sn)₃Fe^II(CN)₆]_n, 6 and [(LiDEE)_0.9(Me₃Sn)₃Fe _o.1 ^III Fe _o.9 ^II (CN)₆]_n, 7. The stoichiometry and nature of the guest depend on the type of the metal iodide and the reaction conditions. The polymeric nature of these SCP is due to the presence of trigonal bipyramidal configured structure which bridges between the single d-transition metal ions. The host–guest SCP containing the Li ions have been tested as electrodes to construct four different lithium-ion batteries.     

Structure of a catalytically active octanuclear cobalt complex [Co(II)4Co(III)4(μ4-O)4(μ-O2CPh)12(PhCOOH)4]

The structure of a catalytically active octanuclear mixed-valence cobalt complex [Co(II)₄Co(III)₄(μ₄-O)₄(μ-O₂CPh)₁₂(PhCOOH)₄] (Ph = phenyl, C₆H₅) has been determined using an X-ray diffraction analysis. The presence of 16 ligands containing phenyl rings in each complex gives rise to strong steric stresses and leads to a disordering of terminal groups. The compound crystallizes in the monoclinic crystal system, space group of symmetry P2₁/n, with the unit cell parameters a = 18.076(5) ?, b = 26.371(3) ?, c = 22.791(5) ? β = 92.48(1)°, V = 10853(4) ?³, Z = 4, and ρ = 1.516 g/cm³. The final values of the discrepancy factors are R1 = 0.0441 for 4005 symmetrically nonequivalent reflections with I ≥ 2σ(I), wR2 = 0.1131, and GooF = 0.943.     

Complexes Containing N-(2-hydroxyethyl)-ethylenediamine with Tetracyanometallate (II): Synthesis, IR Spectra, Thermal Behavior, Crystal Structure, Magnetic Properties and Catalysis

Two novel cyano-bridged Ni²⁺ and Cu²⁺ compounds, {[M²⁺(hydeten)₂(μ-CN)₂Ni(CN)₂] _n , M²⁺ = Ni²⁺ (c1) and Cu²⁺ (c2), N-(2-hydroxyethyl)-ethylenediamine (hydeten), were prepared and characterized by elemental analysis, IR spectroscopy and thermoanalytical measurements. The one-dimensional polymeric structure of c2, which was determined by X-ray diffraction techniques, was formed with a 2,2-TT-type chain, –Cu(hydeten)₂-NC-Ni(CN)₂-CN-Cu(hydeten)₂-, linkages. Also, while the EPR spectra and magnetic properties of complexes c1 and c2 with [Ni(hydeten)₂Pd(CN)₄] (c3) and [Cu(hydeten)₂Pd(CN)₄] (c4) [Karadağ, Z Kristallogr 222:39, 2007] were investigated, the catalytic activity of c3 and c4 was studied. The EPR spectra of c2 and c4 showed that Cu²⁺ was located in tetragonal distorted octahedral sites (D _4h ) and the ground state of the paramagnetic electron was d _{x² - y²} d_{{ x^{2} - y^{2} }} . The magnetic behavior exhibited weak antiferromagnetic interactions in all the complexes. Also, the catalytic properties of c3 and c4, which were assigned with Suzuki and Heck coupling reactions, showed that they did not have catalytic effects.     

Two Novel Bimetallic Cyano-Bridged Coordination Polymers Containing the 2,2′-(Ethylenedioxy)bis (Ethylamine): Syntheses,Structural, Thermal and Magnetic Properties

Two new cyano bridged bimetallic polymeric complexes, [Ni(edbea)Ni(CN)₄]·1/2H₂O (1) and [Cu(μ-edbea)(μ-CN)₂ Ni(CN)₂]·H₂O (2) [edbea = 2,2′-(ethylenedioxy)bis(ethylamine)] have been synthesized by adding metal chloride (M = Ni^II and Cu^II), and edbea into [Ni(CN)₄]²⁻ in water–ethanol solution and then characterized by elemental analysis, infrared (IR) and electron paramagnetic resonance (EPR) (for only complex 2) spectra, variable temperature magnetic measurement, and thermal gravimetric analysis. The X-ray diffraction crystal structure of complex 2 shows a 2D polymeric chain –edbea(N5,O1)–Cu1–N1C1–Ni(CN)2–C4N6–Cu1–(N6,O2) edbea– in which the Cu^II centers are linked by two cyano and one edbea. The powder EPR spectrum of the complex 2 has shown that Cu^II ions are located in rhombically distorted octahedral sites. The magnetic properties of the coordination polymers have been studied in temperature range of 15–300 K. The magnetic behaviors investigation of complexes 1 and 2 indicated the presence of a very weak antiferromagnetic interaction.     

Self-assembly of a novel 3D copper(I)-tetrazolate supramolecular framework via interpenetration of porous 2D double-layer motifs

The self-assembly of CuCN and 1H-TAZ ligand under hydrothermal conditions generated a novel three-dimensional hybrid supramolecular framework, namely, [Cu₆(TAZ)₄(CN)₂]_n (1) (TAZ = tetrazole). Single-crystal X-ray diffraction show that [Cu₂(TAZ)₂] binuclear subunits are linked by μ₂- and μ₃-CN groups to give a 2D double-wave-shaped network, which possesses 1D channels with four open-windows. The 2D bilayers interpenetrated each other to form the 3D supramolecular framework of 1.     

A Mixed Valence Copper Cyanide 3D-supramolecular Coordination Polymer Containing 1,10-Phenathorline Ligand as a Potential Antitumor Agent, Effective Catalyst and Luminescent Material

The structure of the 3D-supramolecular coordination polymer (SCP) _∞³{[Cu^Ι(CN)·2(phen)·Cu^ΙΙ(CN)₂·(phen)]·5H₂O}, 1 contains the [Cu^Ι(CN)·2(phen)], [Cu^ΙΙ(CN)₂·(phen)] molecular complexes and five water molecules which are connected with each other by hydrogen bonds. The most intriguing feature in the structure of 1 is the unusual supramolecular interactions, including hydrogen bonds which involve the terminal cyanide and the phenanthroline (phen) ligands and π–π stacking which generate a unique 3D-supramolecular architecture in the solid state. The emission spectrum of 1 displays a band centered at 420 nm which was assigned to S_o-T transition in the CuCN fragments. This band suffers a shift to longer wavelength by about 30 nm than that of CuCN itself. The emission bands at 435, 450, and 475 correspond to the close laying π–π* transitions of the coordinated phen. The main band at 435 nm exhibits a red shift than that of phen by about 70 nm which makes it attractive as luminescent sensor. Also, the SCP 1 was used as heterogeneous catalyst for the degradation of Metanil Yellow (MY) dye by dilute solution of hydrogen peroxide as oxidant. The reaction is first order with respect to the MY dye. The 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) assay was used to determine the in vitro antitumor activity of the SCP 1 on human breast cancer cell line, MCF7. The cytotoxicity of the SCP 1 is more efficient than that of the Doxorubicin (DOX) drug. The thermal stability has been also investigated.     

Assembly, Fluorescence Properties and Antitumor Activity of Novel Silver(I) Cyanide Supramolecular Coordination Polymer Based on Trans-1,2-bis(4-pyridyl)ethene and Me3SnCl

A bimetallic supramolecular coordination polymer; {[(Me₃Sn)₈Ag₄(OH)₄(CN)₈(tbpe)](tbpe)} _n , 1, was obtained by the reaction in situ of K₂[Ag(CN)₂] with Me₃SnCl and trans-1,2-bis(4-pyridyl)ethene (tbpe) in a H₂O/MeCN/NH₃ solvent. The structure of 1 consists of discrete puckered tetranuclear chains comprising {[(Me₃Sn)₄Ag₂(OH)₂(CN)₄]₂(tbpe)} in addition to one template free tbpe ligand. In these chains, the bridging hydroxyl group and the bipodal tbpe ligand are used to give two novel spacers based on the organometallic Me₃Sn unit; i.e., a longer spacer [–CN–(Me₃)Sn–O(H)–(Me₃)Sn–L–(Me₃)Sn–O(H)–(Me₃)Sn–NC–] with a separation distance of 31.29 Å, and a relatively shorter spacer [–CN–(Me₃)Sn–O(H)–(Me₃)Sn–NC–] with a separation distance of 14.431 Å. Supramolecular interactions such as hydrogen bonding, π–π stacking, cation···π interactions, play a prominent role in the assembly of this compound. The structure of the SCP was also investigated by FTIR and electronic absorption spectra and thermal analysis and the data are compared to the prototype compounds. The SCP 1 exhibits strong fluorescence in acetonitrile and shows specific in vitro antitumor activity against human breast cancer cell line, MCF7.     

Supramolecular Design of Coordination Polymers Based on Silver(I) Azide and Nitrogen Donor Ligands

The reactions of K₃[Cu(CN)₄], Me₃SnCl and methylpyrazine (Me-pyz) or tetramethylpyrazine (Me₄-pyz) in water/dioxane system afforded two new coordination polymers (CP); [{Cu(μ-CN)}₂(μ-Me₄-pyz)·dioxane] _n , 1, and [Cu{μ-Mepyz}{μ-CNSn(Me₃)NC–}], 2. X-ray single crystal analysis shows that 1 contains two crystallographically different copper(I) ions which acquire trigonal planar geometry. The structure of 1 contains non-linear (CuCN)_∞ chains that are interconnected by the Me₄-pyz ligands forming 3D-network structure. The structure of 1 has two-fold interpenetrating 3D-networks with dioxane molecules encapsulated in the voids of the structure. The structures of these CP were also investigated by FTIR and mass spectroscopy, thermal analysis and compared with the prototype compounds. Spectroscopic analyses of 2 confirm the presence of all components (Me₃Sn⁺, Cu(CN)₂ ⁻ and Me-pyz) and support the composition predicted by elemental analysis. 1 and 2 display strong fluorescence in the solid state at room temperature.     

3D-Supramolecular Coordination Polymers as Effective Oxidizing Agents Towards 2,4-Dichlorophenol and 2,6-Di-<Emphasis Type="Italic">t</Emphasis>-butylphenol

3D-supramolecular coordination polymers (SCP) of the type [(R₃Sn)₃Fe^III(CN)₆]; R = CH₃ (I), n-Butyl (II) and phenyl (III) contain wide expandable channels capable of encapsulating and in situ oxidizing 2,4-dichlorophenol (DClP) and 2,6-di-t-butylphenol (DBP) to 2-chloro-1,4-benzoquinone (2-ClBQ) and 3,5,3,5-tertra-t-butyl-4,4-diphenoquinone (BDPQ), respectively, to form new host–guest supramolecular coordination polymers (HGSCP) (1–6). The oxidation products are investigated by spectrophotometry and HPLC methods. A kinetic study indicated a first-order reaction with respect to the hosts SCP I–III. The mechanism and rate of oxidation are discussed in relation to the structure of the SCP.     

[(μ-Fluoro) bis{(triphenyl) (p-tolyl) antimony}] iodide

The crystal structure of the mixed halide compound, [Ph₃(p-tolyl)Sb]F_0.5I_0.5 (4), obtained from [Ph₃(p-tolyl)Sb] [BF₄] and NaI, has been determined. Compound 4 is an ionic compound with a novel fluoride bridged cation, [Ph₃(p-tolyl)SbFSb (p-tolyl)Ph₃]⁺, and an independent I⁻ anion. The geometry of the Sb centres in the centrosymmetric cation is distorted trigonal bipyramidal with the axial sites occupied by a phenyl group [SbC(7) = 2.127(8) Å] and the bridging fluoride [SbF = 2.2856 (11) Å]; the C(7)-SbF angle is 177.6(2) °. The average SbC(equatorial) bond length of 2.099 Å is only slightly less than the SbC(axial) bond length.     

Unexpected Formation of a Doubly Bridged Cyclo-1,2-dithian 1D Coordination Cu<Subscript>2</Subscript>I<Subscript>2</Subscript>-Containing Luminescent Polymer

Abstract  

CuI reacts instantaneously with butanedithiol in MeCN solution to form a sparingly soluble and thermally stable colorless polymeric material 1 of composition [(Cu₂I₂){HS(CH₂)₄SH}] _n . Raman and IR spectroscopy confirm the presence of Cu(I) bound S–H functions. Furthermore, small amounts of the yellow compound [{Cu(μ₂-I)₂Cu}(C₄H₈S₂)₂] _n 2 co-crystallize after several days. If the reaction mixture is exposed to air, polymeric 2 is isolated as the main product. An X-ray diffraction study reveals that 1D polymer 2 is assembled by rhomboid Cu(μ₂-I)₂Cu clusters (d Cu···Cu 2.6843(18) ?), which are linked through the S-atoms of six-membered 1,2-dithian heterocycles, thus generating an infinite ribbon. The low-frequency region in the Raman spectra show a striking similarity suggesting that polymers 1 and 2 bear the same cluster rhomboid Cu(μ₂-I)₂Cu clusters. The photophysics and luminescence properties of 2 have been studied experimentally and by means of DFT/TDDFT calculations.