A Low‐dimensional Viologen/Iodoargentate Hybrid [(BV)2­(Ag5I9)]n: Structure,Properties, and Theoretical Study

A new low‐dimensional benzyl viologen/iodoargentate hybrid, [(BV)₂(Ag₅I₉)]_n ( 1 ) (BV²⁺ = benzyl viologen) was prepared. In 1 , (Ag₆I₉)_n^2– chain exhibits a new type of one‐dimensional chain constructed from vertex‐sharing of Ag₅I₁₀ units, and its two‐dimensional layer structure was constructed from C–H ··· I hydrogen bonds. Strong luminescence at 404 nm can be detected in 1 . DFT calculation suggests that 1 displays a reduced bandgap, which is led by a more dispersed LUMO band of BV²⁺ compared with MV²⁺ in [MV(Ag₂I₄)]_n.     

Hybrid nanoflowers bearing tetraphenylporphyrin assembled on copper(II) or cobalt(II) inorganic material: A green efficient catalyst for hydrogenation of nitrobenzenes in water

Simple fabrication of organic–inorganic hybrid nanoflowers (TPP@CuhNfs and TPP@CohNfs) was achieved with tetraphenylporphyrin (TPP) as organic counterpart and Cu²⁺ or Co²⁺ ions as inorganic materials via a green route, with lower cost and controlled pH. The effect of pH levels and TPP concentrations on the morphology of the TPP@CuhNfs and TPP@CohNfs materials was examined by scanning electron microscopy (energy-dispersive X-ray [EDX]). The formation and chemical structures of TPP@CuhNfs and TPP@CohNfs were evaluated using Fourier transform infrared. Elemental analyses of these hybrid nanoflowers were carried out by EDX. The fabricated TPP@CuhNfs and TPP@CohNfs nanomaterials under optimum conditions act as effective reusable catalysts for the hydrogenation of nitroanilines in aqueous media at ambient temperature. The time-dependent hydrogenation can be easily monitored spectrophotometrically and verified by ¹H-nuclear magnetic resonance. These types of the catalytic reaction or system are recorded to be useful toward the hydrogenation of nitroanilines, regardless of the position and type of substrate. Moreover, TPP@CuhNfs and TPP@CohNfs catalysts demonstrated a type of metal ions-dependent catalytic efficiency toward hydrogenation of nitroanilines (organic pollutants), with TPP@CuhNfs found to be more effective than TPP@CohNfs. However, both catalysts containing Cu²⁺ and Co²⁺ ions showed good performance and can be reused at least five times without a significant decline in yield. The presented approach based on hybrid nanoflowers provides as a low cost and ecofriendly method (green route) for different catalytic hydrogenations.     

Synthesis,crystal structure,and characterizations of a 3-D Cu(I) complex with 1,6-bi(benzotriazole)hexane

Solvothermal reaction of the flexible ligand 1,6-bi(benzotriazole)hexane (BBTH) with CuCl generated a 3-D hybrid solid, {[CuCl]₂(BBTH)} _n (1), which was investigated by elemental analysis, FT-IR, X-ray powder diffraction (XRPD), X-ray single-crystal diffraction, TG/DTA, and photoluminescence measurements. Compound 1 crystallizes in the tetragonal system, space group I4(1)/a, a = b = 17.636(2) Å, c = 13.5345(15) Å, V = 4209.6(9) ų, Z = 8. The distorted tetrahedral geometry of Cu(I) is defined by two chlorides and two N donors from different BBTH ligands. Adjacent copper atoms are connected by μ₂-Cl to give a 1-D zigzag inorganic chain, and further linked by BBTH ligands via μ₄-bridging, forming the 3-D hybrid structure of 1. Cu(I) atoms and BBTH ligands can be regarded as two kinds of non-equivalent 4-connected nodes, which lead to an unusual topological network with Schläfli symbol of (3².8.9².10)₂(3².8².9²). Compound 1 exhibits high thermal stability and shows strong red fluorescence emission at 538 nm in the solid state at ambient temperature.     

Dinuclear copper(I) and copper(I)/silver(I) complexes with condensed dithiolato ligands

The Cu(III) complex Pr 4N[Cu{S 2C=( t-Bu-fy)} 2] ( 1) ( t-Bu-fy = 2,7-di- tert-butylfluoren-9-ylidene) reacts with [Cu(PR 3) 4]ClO 4 in 1:1 molar ratio in MeCN to give the dinuclear complexes [Cu 2{[SC=( t-Bu-fy)] 2S}(PR 3) n ] [ n = 2, R = Ph ( 2a); n = 3, R = To ( 3b); To = p-tolyl]. The analogue of 2a with R = To ( 2b) can be obtained from the reaction of 3b with 1/8 equiv of S 8. Compound 2b establishes a thioketene-exchange equilibrium in solution leading to the formation of [Cu 4{S 2C=( t-Bu-fy)} 2(PTo 3) 4] ( 4b) and [Cu 2{[SC=( t-Bu-fy)] 3S}(PTo 3) 2] ( 5b). Solid mixtures of 4b and 5b in varying proportions can be obtained when the precipitation of 2b is attempted using MeCN. The reactions of 1 with AgClO 4 and PPh 3, PTo 3 or PCy 3 in 1:1:4 molar ratio in MeCN afford the heterodinuclear complexes [AgCu{[SC=( t-Bu-fy)] 2S}(PR 3) 3] [R = Ph ( 6a), To ( 6b), Cy ( 6c)]. Complex 6c dissociates PCy 3 in solution to give the bis(phosphine) derivative [AgCu{[SC=( t-Bu-fy)] 2S}(PCy 3) 2] ( 7c), which undergoes the exchange of [M(PCy 3)] (+) units in CD 2Cl 2 solution to give small amounts of [Cu 2{[SC=( t-Bu-fy)] 2S}(PCy 3) 2] ( 2c) and [Ag 2{[SC=( t-Bu-fy)] 2S}(PCy 3) 2] ( 8c). Complexes 6a and b participate in a series of successive equilibria in solution, involving the dissociation of phosphine ligands and the exchange of [M(PCy 3)] (+) units to give 2a or 3b and the corresponding disilver derivatives [Ag 2{[SC=( t-Bu-fy)] 2S}(PR 3) 2] [R = Ph ( 8a), To ( 8b)], followed by thioketene-exchange reactions to give [AgCu{[SC=( t-Bu-fy)] 3S}(PR 3) 2] [R = Ph ( 9a), To ( 9b)]. Complexes 9a and b can be directly prepared from the reactions of 1 with AgClO 4 and PPh 3 or PTo 3 in 1:1:3 molar ratio in THF. The crystal structures of 3b, 6b, 6c, 7c, and 9a have been solved by single-crystal X-ray diffraction studies and, in the cases of 7c and 9a, reveal the formation of short Ag...Cu metallophilic contacts of 2.8157(4) and 2.9606(6) A, respectively.     

A {Ni7} cluster-containing sandwich-type phosphotungstate functionalized by organic bisphosphonate ligands and its two-dimensional supramolecular structure

A {Ni₇} cluster-substituted sandwich-type phosphotungstate Na₁₀（NH₄）₄[{(B-a-PW₉O₃₄)Ni₃ （OH）（H₂O）₂（HAIe）}₂Ni]·22H₂O（1） was syntliesized using the conventional aqueous solution method. Compound 1 represents the first nickel-containing sandwich-type polyoxometalate functionalized by bisphosphonate ligands.Fuither,the sandwich-type polyoxoanions aggregated via the H-bonding interactions into a two-dimensional（2D） supramolecular framework.     

Photocatalytic active silver organic framework: Ag(I)-MOF and its hybrids with silver cyanamide

Probing into the new heterostructure based on metal–organic frameworks (MOFs) and optimizing their photocatalytic efficiency under solar energy irradiation are one of hot topics in extending applications of MOFs in photocatalytic technology. Inspired by the excellent visible-light responses and photocatalytic activities of inorganic silver salts, in this work, we focused on the construction of hybrid photocatalysts involving Ag-MOF and silver cyanamide (Ag₂NCN). Two opposite in situ synthesis routes were adopted, which are hydrothermally producing Ag-MOF in the presence of Ag₂NCN (route A) or precipitating Ag₂NCN in the existence of Ag-MOF (route B), and the mass ratio of Ag₂NCN vs. Ag-MOF was optimized. The morphology and structure character show that the synthetic routes have no obvious influences on the crystal structure, but change the morphology and size of final hybrid photocatalysts. The photocatalytic degradation of Rhodamine B under simulated solar energy has been tested to evaluate the photocatalytic activities for resulting hybrids. Compared to single Ag-MOF and Ag₂NCN, the enhanced photocatalytic rates are represented by the hybrids. The electrochemical analyses and the active species trapping experiments were conducted to clarify the photocatalytic mechanism for resulting hybrids. The good recycling photocatalytic results indicate the prospect applications of Ag-MOF based hybrid photocatalysts.     

Heterometallic Complexes with Gold(I) Metalloligands: Self‐Assembly of Helical Dimers Stabilized by Weak Intermolecular Interactions and Solvophobic Effects

New gold(I) alkynyl metalloligands bpylC?CAuL, bpyl′C?CAuPPh₃, and PPN[Au(C?Cbpyl′)₂] (bpyl or bpyl′=2,2′‐bipyridin‐5‐yl or ?4‐yl, respectively; L=PMe_xPh_3?x (x=1–3), P(C₆H₃Me₂‐3,5)₃, PCy₃, XyNC) have been synthesized. Ligands bpylC?CH and metalloligands bpylC?CAuL (L=PPh₃, PMePh₂, PCy₃, CNXy) react with MX₂ (M=Fe, Zn, X=ClO₄; M=Co, X=BF₄) to give complexes [M(bpylC?CZ)₃]X₂ (Z=H or AuL). In most cases, these complexes are mixtures of fac and mer isomers in a statistical distribution, in both CH₂Cl₂ and MeCN. However, for L=PPh₃, the fac isomer is dominant in MeCN. NMR and ESI‐MS studies, together with the crystal structure of [Co(bpylC?CAuPPh₃)₃](BF₄)₂, suggest that this solvent dependence is originated by the formation of helical dimers between two fac complexes in MeCN. These dimers are stabilized by solvophobic effects and multiple intermolecular interactions. Complex [Fe(Ph₃PAuC?CbpdiylC?CAuPPh₃)₃](ClO₄)₂ (bpdiyl=2,2′‐bipyridin‐5,5′‐diyl) was obtained by reaction of three diauro diethynylbipyridines and Fe(ClO₄)₂.     

O-Complexes of 1,3,2,5-dioxaboraphosphorinanes with copper(I) and silver(I) salts

1,3,2,5-Dioxaboraphosphorinanes interact stereospecifically with Cu(I) and Ag(I) salts to form the corresponding O-complexes. The three-dimensional structure of the ligands has been established from³¹P NMR and¹H NMR data.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 4, pp. 906–912, April, 1991.     

Synthesis,Crystal Structure,and Optical Properties of (CH3NH3)2CoX4 (X = Cl,Br, I,Cl0.5Br0.5, Cl0.5I0.5, Br0.5I0.5)

The reaction of methylammonium halides and cobalt halides yielded the organic‐inorganic hybrid compounds of general formula (CH₃NH₃)₂CoX₄. By varying the different halides, we were able to synthesize the whole row from Cl to I as well as some mixed halides compounds and to determinate the crystal structures. (CH₃NH₃)₂CoX₄ (X = Cl, Br, Cl_0.5Br_0.5, Br_0.5I_0.5) crystallize isotypic to (CH₃NH₃)₂HgCl₄ in space group P2₁/c with Z = 4 [X = Cl: a = 7.6483(9), b = 12.6885(18), c = 10.8752(12) Å, β = 96.639(9)°; X = Cl_0.5Br_0.5: a = 7.8271(9), b = 12.9543(9), c = 11.1007(11) Å, β = 96.320(8)°; X = Br: a = 7.9782(2), b = 13.1673(2), c = 11.2602(2) Å, β = 96.3260(10)° and X = Br_0.5I_0.5: a = 8.2435(12), b = 13.645(2), c = 11.5856(18) Å, β = 95.54(2)°]. The mixed halides show a statistic distribution in both cases. In (CH₃NH₃)₂CoCl₂I₂ an ordered variant is realized representing a new structure type [C2/m, Z = 4, a = 18.808(4), b = 7.3604(7), c = 10.4109(17) Å, β = 120.364(13)°]. (CH₃NH₃)₂CoI₄ crystallizes again isotypic to the respective mercury compound [(CH₃NH₃)₂HgCl₄] [Pbca, Z = 8, a = 10.9265(5), b = 12.1552(5), c = 20.9588(9) Å]. All structures are build up by inorganic tetrahedral [CoX₄]^2– anions and organic (CH₃NH₄)⁺ cations. Additionally the Raman spectra as well as the optical reflectance spectra are discussed.     

A new 1-D chain based on the trivacant monocapped Keggin arsenomolybdate and the copper complex linker: synthesis,crystal structure,and ESI-MS analyses

A new organic–inorganic hybrid (H₂en)₂[[Cu(en)₂]As^IIIAs^VMo^VI₉O₃₄]·6H₂O (1), containing a 1-D helical chain based on the trivacant monocapped Keggin arsenomolybdate and the copper complex linker {[Cu(en)₂][As^IIIAs^VMo^VI₉O₃₄]}_n^4n? (en = ethylenediamine), has been synthesized and characterized by IR spectra, TG analyses, single-crystal X-ray diffraction, and high-resolution electrospray ionization mass spectrometry (ESI-MS). Large voids are observed and a 1-D chain containing repeated (H₂O)₈ water units from lattice water molecules is formed along the a axis in the crystal structure. The high-resolution ESI-MS shows that the intact framework [Cu(en)₂][As^IIIAs^VMo^VI₉O₃₄]^4? exists in solution.     

Synthesis,crystal structure,vibrational, optical properties,and a theoretical study of a new Pb(II) complex with bis(1-methylpiperazine-1,4-diium): [C5H14N2]2PbCl6·3H2O

An investigation of the solid-state X-ray structure of the new organic–inorganic compound [C₅H₁₄N₂]₂PbCl₆·3H₂O shows a layered organization of the (PbCl₆)^4– anions, with (R₂NH₂)⁺ groups and water molecules developed in the [001 A. Hu, H.L. Ngo, W. Lin. J. Am. Chem. Soc., 125, 11490 (2003).[Crossref], [PubMed], [Web of Science ®] , [Google Scholar]] plane at x = (2n?+?1)/4. The crystal structure is stabilized by N???H···Cl, N???H···O, O???H···Cl, O???H···O, and C???H···Cl hydrogen bonds. The powder X-ray diffraction and X-ray photoelectron spectroscopic (XPS) analyses confirm the phase purity of the crystal sample. The intermolecular contacts are quantified using the Hirshfeld surfaces computational method. The major inter-contacts contributing to the Hirshfeld surfaces are H…Cl, H…H, and O…H. The vibrational modes were identified and assigned by IR and Raman spectroscopies. The optical properties were investigated by UV–visible and photoluminescence spectroscopic studies. The compound was characterized by thermal analysis to determine its thermal behavior with respect to the temperature. Finally, X-ray photoelectron spectroscopy analysis is reported for analyzing the surface chemistry of [C₅H₁₄N₂]₂PbCl₆·3H₂O.     

Tetraphosphinitoresorcinarene complexes: dynamic clusters with silver(I) and copper(I) halides

Silver(I) and copper(I) halide derivatives of several tetrakis(diphenylphosphinito)resorcinarene ligands are reported. The complexes [resorcinarene(O(2)CR)(4)(OPPh(2))(4)(M(5)X(5))], with resorcinarene = (PhCH(2)CH(2)CHC(6)H(2))(4), R = C(6)H(11), 4-C(6)H(4)Me, C(4)H(3)S, OCH(2)CCH, or OCH(2)Ph, M = Ag, X = Cl, Br, or I, M = Cu, and X = Cl or I, contain a crownlike [P(4)M(5)X(5)] metal halide cluster. These crown clusters were found to be dynamic in solution, as studied by variable-temperature NMR, and easily fragment to give the corresponding complexes containing [P(4)M(4)X(5)](-) and [P(4)M(2)(micro-X)](+) units. Reaction of pentasilver crown clusters with triflic acid gave the corresponding disilver complexes [resorcinarene(O(2)CR)(4)(OPPh(2))(4)]Ag(2)(micro-Cl)]]CF(3)SO(3). Thus, these resorcinarene-based ligands act as a platform for the easy and reversible assembly of copper(I) and silver(I) clusters with novel structures.     

Deep eutectic silsesquioxane hybrids with quaternary ammonium/urea derivatives: synthesis and physicochemical and ion-conductive properties

We report the synthesis of deep eutectic silsesquioxane hybrids (DE-SQs) by simple mixing of quaternary-ammonium-containing SQ and urea derivatives. Cationic SQ, which was prepared by the hydrolytic condensation of a triethoxysilane precursor derived from 2-(dimethylamino)ethyl acrylate, followed by a quaternization reaction with methyl iodide, was used as a quaternary-ammonium-containing SQ component. Cationic SQ reacted with urea at a 1:2 M ratio at 80 °C for 48 h to yield a viscous DE-SQ (2Urea) liquid with a low glass transition temperature (T_g = ?11 °C). Urea derivatives—1,3-dimethylurea (DMU) and 1,3-dimethylthiourea (DMTU)—were additionally used as hydrogen bond donors to form low-T_g DE-SQs. The thermal, physical, and ion-conductive properties of the DE-SQ family of organic–inorganic hybrids were investigated and characterized, and the influences of the nature of the urea derivative and their feed ratios on DE-SQ formation were evaluated. Among the DE-SQs developed in this study, DE-SQ (2Urea) and DE-SQ (2DMTU) achieved the highest ionic conductivity, with DE-SQ (2Urea) exhibiting 2.35 × 10^?6 and 6.63 × 10^?4 S cm^?1 at 25 and 75 °C, respectively, under anhydrous conditions. This is the first report on the synthesis of DE-SQs by simple mixing of two solids, wherein the resulting compounds exhibit low T_g, thermal stability, and characteristic ionic conductivity. The ability to incorporate unique DE units into the SQ structure facilitates the development of advanced organic–inorganic hybrid materials possessing a wide range of functions and applications.     

The solution stability of copper(I) and silver(I) complexes with N-heterocyclic carbenes

The tris-benzimidazolium cage LH(3)(3+), in MeCN solution, in the presence of OH(-), forms with Cu(I) and Ag(I) ions complexes of formula [M(I)(LH)](2+), in which each metal is linearly coordinated by two carbenes and one imidazolium N-H fragment remains intact. To achieve two-coordination, the two N-heterocyclic moieties of the cage make a saloon-door type motion, with a conformationally costless rotation of ca. 30° each. The two [M(I)(LH)](2+) complexes show high thermodynamic stability and are inert with respect to metal substitution, due to the mechanical constraints imposed by the ligating framework. Complexation with Cu(I) and Ag(I) with the reference unidentate carbene ligand Q, derived from the benzimidazolium precursor QH(+), was studied for comparison. Both metals in MeCN form 1:1 and 1:2 complexes with the carbene ligand Q according to two stepwise equilibria. Q complexes of both metals are labile with respect to metal substitution and those of Ag(I) are more stable than those of Cu(I). A significant cooperative effect has been observed with the formation of the [Ag(I)Q(2)](+) complex.     

Reactivity of ZrO(MFP) and ZrO(RP) Nanoparticles with LnCl3 for Solvatochromic Luminescence Modification and pH-Dependent Optical Sensing

The luminescence of the inorganic–organic hybrid nanoparticles ZrO(MFP) (MFP=methylfluorescein phosphate) and ZrO(RP) (RP=resorufin phosphate) was modified by addition of different rare earth halides LnCl₃. The resulting composite materials form dispersible nanoparticles that exhibit modified nanoparticle fluorescence depending on the rare earth ion. The resulting chromaticity of the luminescence is further variable by the employment of different solvents for ZrO(MFP)-based composite systems. The strong solvatochromic effect of the MFP chromophore leads to different luminescence chromaticities of the composite materials between green, yellow, and blue in THF, toluene, and dichloromethane, respectively. The luminescence of ZrO(RP)-based composite particles can be modified between the red and blue spectral regions in dependence on the applied reaction temperature. Beside a luminescence shift that is derived from nanoparticle modification by LnCl₃, a strong turn-on effect of ZrO(RP) particles results after contact with different Brønsted acids and bases in combination with a respective chromaticity shift. Both effects enable the potential employment of such particles as highly sensitive optical pH sensors.     

Organic‐inorganic Hybrid Lanthanide‐Silver Heterometallic Coordination Frameworks Constructed from Oxalate and Sulfate Anion: Syntheses,Structures, and Photoluminescent Properties

The first four examples of organic‐inorganic hybrid lanthanide‐silver heterometallic frameworks, namely, [AgLn(μ₅‐C₂O₄)(SO₄)(H₂O)₂] [Ln = Eu ( 1 ) and Sm ( 2 )] and [AgLn(μ₄‐C₂O₄)_0.5(μ₆‐C₂O₄)_0.5(SO₄)(H₂O)] [Ln = Tb ( 3 ) and Dy ( 4 )] based on oxalate and sulfate anions were synthesized by hydrothermal reactions of lanthanide oxide, silver nitrate, oxalic acid and sulfuric acid. All structures contain ladder‐like inorganic lanthanide sulfato chains, which are further connected together through silver atoms by oxalate anions with different coordination behavior (μ₅‐C₂O₄: 1 and 2 , μ₆‐C₂O₄ mixed μ₄‐C₂O₄: 3 and 4 ) to generate two types of 3D networks. The luminescent properties of these compounds were also studied.     

New heterometallic coordination polymers based on zinc(II) complexes with Schiff-base ligands and dicyanometallates: synthesis,crystal structures,and luminescent properties

Four new d¹⁰ heterometallic coordination polymers have been obtained using three Schiff-base ligands, zinc(II) nitrate, and dicyanometallates: ₁^∞[{Zn₃(Salen)₂}{μ-Au(CN)₂}₂] (1); ₁^∞[Zn(Saldmen){μ-Ag(CN)₂}]·2H₂O (2); ₁^∞[Zn(Salampy){μ-Ag(CN)₂}] (3); ₁^∞[Zn(Salampy){μ-Au(CN)₂}] (4). The Schiff bases are obtained from condensation of salicylaldehyde with ethylenediamine (H₂Salen); N,N-dimethyl-ethylenediamine (HSaldmen) and, respectively, 2-aminomethyl-pyridine (HSalampy). The dicyanometallates are K[Ag(CN)₂] and K[Au(CN)₂]. The compounds were characterized by X-ray single-crystal diffraction, infrared spectroscopy, UV–vis spectroscopy, and elemental analysis. In compound 1, the homotrimetallic units, {Zn₃(salen)₂}²⁺, are connected by two [Au(CN)₂]^? bridges, forming a 1-D double chain. In compounds 2–4, the crystal structures show polymeric zigzag chains generated by the mononuclear zinc(II) nodes and [M(CN)₂]^? spacers. The luminescence properties of the new heterometallic polymers have also been investigated.