Inorganic Chemistry Communications (v.14, #11)

Contents List (iii-xi).

A new 3D metal-organic framework [Cu(en)(ntd)](e-urea)(H2O) (1; en = 1,2-ethylenediamine, ntd = 1,4-Naphthalenedicarboxylic acid, e-urea = 2-imidazolidinone hemihydrate), has been synthesized by urothermal method. Structural analysis shows that compound 1 possesses unprecedented (3,4)-connected tfi topology. 2-imidazolidinone, one of the urea derivatives, plays multiple roles in the self-assembly of compound 1.A new 3D metal-organic framework with in situ generated ligand was synthesized urothermally and structurally characterized as a (3,4)-connected tfi network.Display Omitted► Urothermal synthesis of a metal organic framework/ ► The metal organic framework with unusual (3,4)-connected tfi topology/ ► In situ ligand synthesis from 2-imidazolidinone to 1,2-ethylenediamine.
Keywords: Urothermal synthesis; 2-imidazolidinone; Topology; Metal organic framework; Crystal structure;

A new organic–inorganic hybrid compound based on lanthanide-organic chain and Keggin-type polyoxometalate by Xiu-Li Hao; Ming-Fa Luo; Xin Wang; Xiao-Jia Feng; Yang-Guang Li; Yong-Hui Wang; En-Bo Wang (1698-1702).
The reaction between a double-betaine-containing ligand and DyH[PMo11VO40]·nH2O led to a new polyoxometalate-based lanthanide-organic hybrid compound with the molecular formula [Dy(HL)(L)1.5(H2O)3][PMo11VO40]·8H2O (1) (L = 1,4-bis(pyridinil-4-carboxylato)-l,4-dimethylbenzene). Compound 1 was characterized by elemental analyses, TG, IR, XPS and the single-crystal X-ray diffraction. Compound 1 possesses a cationic 1D polymeric chain [Dy(HL)(L)1.5(H2O)3]n 4n+ with cyclic-, chain- and semi-cyclic-like fragments, corresponding to three different configurations of the double-betaine-containing ligand. These 1D chains are connected together by the H-bonds and π–π interactions to form a 3D supramolecular framework, encapsulating the vanadium-substituted Keggin-type polyoxoanions [PMo11VO40]4−and the solvent molecules. This composite compound displays electrocatalytic activities towards the reduction of nitrite and the luminescent property.The reaction between a double-betaine-containing ligand and LnHPMo11VO40·nH2O leads to a new polyoxometalate-based lanthanide-organic hybrid chain.Display Omitted► In this study we report a new polyoxometalate(POM)-based lanthanide-organic hybrid compound. ► The exchange of POMs can tune the structure of the lanthanide-organic coordination fragments. ► Interestingly, the betaine-containing ligands in 1 exhibit three different configurations. ► Compound 1 displays both luminescent and electrocatalytic activities.
Keywords: Polyoxometalate; Lanthanide-organic chain; Betaine; Electrocatalysis;

Disulfide struts: Assembly motifs supporting a cuprocapsule by Edwin C. Constable; Guoqi Zhang; Catherine E. Housecroft; Jennifer A. Zampese (1703-1705).
Condensation of 2-aminoethanethiol with 1,3-bis(3-formyl-2-hydroxyphenyl)-1,4,7,10,13-pentaoxatridecane in the presence of Cu(OAc)2 and base is accompanied by oxidative coupling of pendant thiols with the formation of a disulfide-containing macrocycle H2 1. This assembles the novel capsule [Cu2(1)2] which hosts two CH2Cl2 guest molecules.During the condensation of 2-aminoethanethiol with 1,3-bis(3-formyl-2-hydroxyphenyl)-1,4,7,10,13-pentaoxatridecane in the presence of Cu(OAc)2, oxidative coupling of the thiol functionalities produces a disulfide-containing macrocyclic ligand H21 which binds copper(II), forming the molecular capsule [Cu2(1)2] which hosts two CH2Cl2 molecules.Display Omitted► Self assembly of a molecular capsule. ► Oxidative thiol coupling to give disulfide bridges that close a macrocyclic ligand. ► Host-guest interactions.
Keywords: Copper; Disulfide; Crystal structure; Capsule; Macrocycle;

Stabilization of gold(III) with bis(pyrazol-1-yl)amine by Tebogo V. Segapelo; Ilia A. Guzei; Lara C. Spencer; James Darkwa (1706-1710).
Bis(3,5-R2pyrazol-1yl)amine (R = H (L1), Me (L2), tBu (L3)) reacts with H[AuCl4] to form the three salts [AuL1][AuCl4]2 (1), [AuL2][AuCl4]2 (2) and [AuL3]Cl2 (3) respectively. The composition of these salts was established via mass spectrometry and microanalysis and confirmed by single crystal X-ray studies for 2. Room temperature 1H NMR spectrum of these salts after a D2O wash showed two triplets for the inequivalent CH2 groups in the ligand backbone, while prior to the D2O washing the 1H NMR spectrum indicated interactions of the amine proton with this two CH2 groups.Bis(pyrazolyl)amine compounds are able to stabilize gold(III) to form salts that have bis(pyrazol-1-yl)aminegold(III) cation, and either tetrachloroaurate or chloride anion.Display Omitted► Bis(pyrazolyl)amine are used to stabilize gold(III). ► This represents the first use of bis(pyrazolyl) ligands to form gold(III) salts. ► Anions are either tretrachloroaurate or chloride.
Keywords: Bis(pyrazol-1-yl)aminegold(III) cation; Tetrachloroaurate and chloride anion; Crystal structure;

Synthesis, characterization of bulky aluminium alkoxide and application in the ring-opening polymerization of ε-Caprolactone by Xiaozhe Yang; Lei Wang; Lihui Yao; Jinfeng Zhang; Ning Tang; Cheng Wang; Jincai Wu (1711-1714).
The reaction of 2,2′-dihydroxy-3,3′,5,5′-tetra-tert-butyl-1,1′-diphenyl (TBBP-H2) with AlMe3 in tetrahydrofuran gives [(TBBP)Al(CH3)(THF)] (1) in high yield. 1 further reacts with 2-propanol to afford dimeric aluminium complex [(TBBP)Al(μ-O i Pr)]2 (2). Catalytic studies of complex 2 indicate that 2 can efficiently initiate the ring-opening polymerization of ε-Caprolactone under a controlled manner, yielding polymers with narrow molecular weight distribution.The reaction of 2,2′-dihydroxy-3,3′,5,5′-tetra-tert-butyl-1,1′-diphenyl (TBBP-H2) with Al(Me)3 and i PrOH in a ratio of 1:1:1:1 in n-hexane gives complex of [(TBBP)Al(μ-O i Pr)]2 (2). Experimental results show that complex 2 is an efficient catalyst for the ring-opening polymerization of ε-Caprolactone with “living” and “immortal” characters.Display Omitted► Aluminium complexes supported by TBBP2− ligand have been prepared and fully characterized. ► Fine crystals 1 and 2 were obtained by crystallization from THF and toluene. ► Complex 2 catalyzes the polymerization of ε-Caprolactone with “living” and “immortal” characters.
Keywords: Aluminium complex; ε-Caprolactone; Catalyst; Ring-opening polymerization;

Synthesis, structure, and luminescent property of a novel cadmium (II) phosphonate with a 3D framework structure using 1,4-benzenedicarboxylic acid as second linker by Chao Li; Jing Li; Zhen-Gang Sun; Kai Chen; Cheng-Lin Wang; Cheng-Qi Jiao; Fei Tong; Yan-Yu Zhu; Cui-Ying Huang (1715-1718).
By using the N-morpholinomethylphosphonic acid as the phosphonate ligand and 1,4-benzenedicarboxylic acid as the second metal linker, a novel cadmium(II) phosphonate with a 3D framework structure, namely, [Cd2(HL)(bdc)(Hbdc)] (1) (H2L=O(CH2CH2)2NCH2PO3H2, H2bdc = HOOCC6H4COOH) has been synthesized under hydrothermal conditions. In compound 1, the {CdO6} and {CdO7} polyhedra are interconnected by phosphonate groups into a 1D chain, each chain is connected by the bdc2− anions into a 2D layer, and the adjacent layers are further linked via the bdc2− anions to form a 3D framework structure with a 1D channel system along the a-axis. Luminescent property of compound 1 has also been studied.A novel cadmium(II) phosphonate with a 3D framework structure, namely, [Cd2(HL)(bdc)(Hbdc)] (H2L = O(CH2CH2)2NCH2PO3H2, H2bdc = HOOCC6H4COOH) 1 has been synthesized by hydrothermal reaction at 160 °C and structurally characterized by single crystal X-ray diffraction, infrared spectroscopy, elemental and thermogravimetric analysis. Luminescent property of compound 1 has also been studied. Display Omitted► A novel cadmium(II) phosphonate with a 3D framework structure has been synthesized and characterized. ► It is for the first time that H2bdc was introduced to construct metal(II) phosphonates assembled from O(CH2CH2)2NCH2PO3H2. ► The compound 1 is a good candidate for blue-light luminescent material.
Keywords: Metal phosphonates; Crystal structure; Cadmium; Luminescent property;

Polymer-based fluorescent sensor incorporating 2,2′-bipyridyl and benzo[2,1,3]thiadiazole moieties for Cu2+ detection by Yu Dong; Biyhaliy Koken; Xiao Ma; Lu Wang; Yixiang Cheng; Chengjian Zhu (1719-1722).
The polymer was synthesized by the polymerization of 4,4′-((4-iodophenoxy)methyl)-2,2′-bipyridine (M-1) with 4,7-diethynylbenzo[2,1,3]-thiadiazole (M-2) via Pd-catalyzed Sonogashira reaction. The fluorescence responses of the polymer towards various transition metal ions were investigated by fluorescence spectra and UV–Vis spectra. The polymer shows green fluorescence under ultraviolet lamp, which can be quenched by Cu2+ completely due to the heavy metal effect. The results suggested that the polymer can be used as a Cu2+-selective sensor via a naked eyes detecting mode.The polymer shows a strong fluorescence emission centered at 515 nm. With the addition of Cu2+ from 0.05 to 0.50 molar ratio, the fluorescence intensity was quenched steadily.Display Omitted► A polymer-based fluorescent sensor is synthesized via Sonogashira coupling reaction. ► The sensor exhibits high sensitivity and selectivity towards Cu2+. ► The fluorescence changing can be easily detected by naked eyes under ultraviolet lamp.
Keywords: Polymer; Fluorescent sensor; Benzo[2,1,3]thiadiazole; Cu2+ detection;

Microwave synthesis of NaLa(MoO4)2 microcrystals and their near-infrared luminescent properties with lanthanide ion doping (Er3+, Nd3+, Yb3+) by Jingchao Zhang; Xiaofeng Wang; Xinhao Zhang; Xudong Zhao; Xiaoyang Liu; Liping Peng (1723-1727).
The doubled metal molybdate NaLa(MoO4)2 microcrystals with various morphologies have been synthesized using microwave assisted hydrothermal method without any organic additives or surfactants. Its morphology and size can be tuned by the initial concentrations of the reagents and the reaction temperatures. Remarkably, the morphologies were the rod, the highly branched dendrite, the ellipsoid-like, when the initial concentration of the precursors was increased from 0.01 to 0.05 M at 180 °C; the morphology can be changed from the octahedral bipyramid to the dendrite when the reaction temperature was increased from 100 to 180 °C at 0.02 M of the reagents. The luminescent properties of the lanthanide ion (Nd3+, Er3+, Yb3+) doped NaLa(MoO4)2 microcrystals were studied, and all of them exhibited strong near-infrared luminescence emissions.NaLa(MoO4)2 microcrystals with various morphologies of the crystal included rod-like, denderite, ellipsoid-like, and bipyramid shapes was synthesized via a microwave-assisted hydrothermal process, and the dendrite morphology of NaLa(MoO4)2 was scarcely reported before. The lanthanide ions (Nd3+, Er3+, Yb3+) doped NaLa(MoO4)2 present strong NIR emission.Display Omitted► Microwave assisted hydrothermal method to synthesis NaLa(MoO4)2 crystals. ► Various morphologies can be achieved simply. ► The sample present good NIR luminescence properties through lanthanide ions doped.
Keywords: NaLa(MoO4)2; Microcrystal; Morphology; Microwave synthesis; NIR luminescence;

Slow magnetic relaxation in lanthanide complexes with chelating imino nitroxide radicals by Xiao-Ling Wang; Hai-Xia Tian; Yue Ma; Pei-Pei Yang; Li-Cun Li; Dai-Zheng Liao (1728-1731).
Two lanthanide-radical complexes [Tb(hfac)3(IM-2py)] (1) and [Tb(hfac)3(IM-2thz)] (2) (hfac = hexafluoroacetylacetonate; IM-2py = 2-(2′-pyridyl)-4,4,5,5-tetramethyl- imidazoline-1-oxyl; IM-2thz = 2-(2′-thiazolyl)-4,4,5,5-tetramethylimidazoline-1-oxyl) have been synthesized. Single crystal X-ray diffraction analysis reveals that complexes 1 and 2 are mononuclear complexes in which the IM-2py/IM-2thz radical is coordinated to the Tb(III) ion in a chelating way. The similar magnetic behavior is observed for two compounds through direct current magnetic measurements, implying antiferromagnetic coupling between Tb(III) and imino nitroxide radical. Alternating current magnetic susceptibility studies show that both complexes exhibit frequency-dependent out-of-phase signals indicative of a slow relaxation of magnetization.Two imino nitroxide radical-Tb(III) complexes have been synthesized. In two complexes, the imino nitroxide coordinates to the Tb(III) ion as chelating ligand. Both complexes show slow relaxation of magnetization.Display Omitted► It is the first time to use chelating imino nitroxide ligands to synthesize the SMM. ► Two complexes exhibit the slow magnetic relaxation resembling SMM behavior. ► To explore the magnetic relaxation, the ferromagnetic interaction is favorable.
Keywords: Imino nitroxide radical; Lanthanide; Slow magnetic relaxation; Crystal structure;

Zirconium (IV) tetradentate Schiff base (salphen) complex has been successfully used for efficient synthesis of wide variety of indole derivatives in EtOH as a standard green solvent under mild conditions. The investigation of turnover number and reusability of the catalyst indicate well the high efficiency and relative stability of the Zr-complex in this reaction.The catalytic activity of Zr(salphen)Cl2 in synthesis of wide variety of indol derivatives in ethanol under mild conditions were developed. The investigation of turnover number and reusability of the catalyst indicate well the high efficiency and relative stability of the Zr-complex in this reaction.Display Omitted► Zirconium (IV) salphen complex catalyzes the synthesis of indoles derivatives. ► The employment of ethanol as an environmentally benign solvent. ► High turnover numbers and reusability of the catalyst makes it a practical strategy.
Keywords: Indole derivatives; Salphen; Schiff base; Zirconium complexes;

Zinc complexes of chiral ligands obtained from methylbenzylamine by María Frutos Pastor; Todd J.J. Whitehorne; Paul O. Oguadinma; Frank Schaper (1737-1741).
Condensation of S-methylbenzylamine with 2 equiv. of 2,4-tert-butylphenol yielded the chiral tridentate ligand 2H2, which formed the dimetallic complex (2)(k-N,(μ-O)2ZnEt)((μ-O)2ZnEt), 3, upon reaction with ZnEt2. Reaction of the chiral Schiff base ligand, 4H, obtained from condensation of salicylaldehyde and S-methylbenzylamine, with ZnEt2 yielded (4)2Zn, 5, or (4)ZnEt, 6, respectively. Deprotonation of 4H with NaH afforded tetrameric {(4)Na}4, 7. Complexes 3, 5 and 7 were characterized by single crystal diffraction studies and tested as initiators in the polymerization of rac-lactide. Complexes 3 and 5 showed only low to moderate activity. All complexes yielded essentially atactic polymers with minor contents of heterotactic enchainment.Several zinc complexes with chiral ligands based on S-methylbenzylamine were synthesized and characterized by X-ray diffraction analysis. They proved to be active, but unselective catalysts for the polymerization of rac-lactide.Display Omitted► Synthesis and characterization of a new tridentate, chiral ligand. ► Synthesis and characterization of 3 chiral zinc complexes and one chiral sodium complex. ► X-ray diffraction studies on 3 of these complexes. ► Application of 3 of these complexes in rac-lactide polymerization.
Keywords: Schiff base ligand; Zinc complexes; Chiral ligands; Lactide polymerization;

Straightforward and efficient oxidation of tris(aryloxide) and tris(amide) uranium(III) complexes using copper(I) halide reagents by Robert K. Thomson; Christopher R. Graves; Brian L. Scott; Jaqueline L. Kiplinger (1742-1744).
Reaction of the trivalent uranium complex U(O-2,6- t Bu2C6H3)3(THF) (4) with copper(I) iodide affords the corresponding uranium(IV) mixed iodide–aryloxide complex (I)U(O-2,6- t Bu2C6H3)3(THF) (5). The oxidative functionalization protocol can also be extended to the synthesis of (Cl)U[N(SiMe3)2]3 (7) from the reaction of the tris(amide) uranium(III) complex U[N(SiMe3)2]3 (6) with copper(I) chloride. These represent the first examples of Cu-based oxidative functionalization of simple trivalent uranium coordination complexes supported by non-metallocene ligand frameworks. With several advantages over existing oxidation methods for uranium tris(aryloxide) and tris(amide) complexes, this Cu-based procedure promises to be a useful and versatile synthetic protocol for uranium chemistry. The X-ray crystal structure of (I)U(O-2,6- t Bu2C6H3)3(THF) (5) is also reported and represents a rare example of a structurally characterized 5-coordinate uranium aryloxide complex. In the solid-state, complex 5 adopts a distorted square pyramidal geometry about the uranium atom, with the iodide ligand occupying the axial position and the THF and three 2,6-di-tert-butylphenoxide ligands occupying the sites of the square pyramid base.Oxidative functionalization of uranium(III) tris(aryloxide) and tris(amide) complexes with copper(I) halides provides convenient access to uranium(IV) mixed-ligand coordination complexes of the type (X)U(OAr)3(THF) and (X)U(NR2)3 (where X = halogen), respectively. These represent the first examples of Cu-based oxidative functionalization of simple trivalent uranium coordination complexes supported by non-metallocene ligand frameworks.Display Omitted► Demonstrate that copper halide oxidations are not limited to uranium complexes supported by metallocene frameworks. ► Report the first copper halide oxidations of simple uranium tris(aryloxide) and tris(amide) complexes. ► Oxidative functionalization used to prepare a U(IV) tris(aryloxide)–iodide complex. ► Oxidative functionalization used to prepare a U(IV) tris(amide)-chloride complex. ► Report a rare example of a structurally characterized 5-coordinate uranium aryloxide complex, (I)U(O-2,6- t Bu2C6H3)3(THF).
Keywords: Uranium; Aryloxide; Amide; Copper halide; Oxidative functionalization; X-ray crystallography;

A bimetallic oxide network constructed from oxomolybdoarsonate clusters and copper(II)-tetrapyridylpyrazine building blocks by Kari Darling; Eric M. Burkholder; Steven Pellizzeri; Max Nanao; Jon Zubieta (1745-1748).
The hydrothermal reaction of Cu(CH3CO2)2·H2O, MoO3, tetrapyridylpyrazine (tpyprz), and 2-hydroxypropyl-1,3-diarsonic acid provided green crystals of the bimetallic oxide phase [{Cu2(tpyprz)(H2O)}Mo6O18(H2O){O3AsCH2CH(OH)CH2AsO3}]·5.5H2O (1·5.5H2O). The two-dimensional structure of 1·5.5H2O is constructed from {Mo6O18(H2O)(O3AsR)2} n 4n  − chains linked through {Cu2(tpyprz)(H2O)}4+ rods into a network. The hexanuclear molybdate ring consists of a tetrad of edge-sharing {MoO6} octahedra that adopt the corner-sharing mode to a diad of face-sharing Mo octahedra. Crystal data for C27H37As2Cu2Mo6N6O32.5: monoclinic P21/c, fw = 1818.18, a = 13.1304(9) Å, b = 21.701(1) Å, c = 17.408(1) Å, β = 100.046(1)°, V = 4884.2(6) Å3, Z = 4, Dcalc = 2.472 g cm− 3, R1  = 0.0669.Hydrothermal chemistry was used to prepare [{Cu2(tpyprz)(H2O)} Mo6O18(H2O){O3AsCH2CH(OH)CH2AsO3}]·5.5H2O, a two-dimensional material constructed from molybdoarsonate chains linked through {Cu2(tpyprz)(H2O)}4+ rods.Display Omitted► Self-assembly of a two-dimensional bimetallic network. ► Embedding of hydrated hexanuclear molybdoarsonate clusters. ► Selective intercalation of alcohols by dehydrated material.
Keywords: Bimetallic oxide; Copper–molybdodiarsonate material; Organic–inorganic hybrid material; X-ray structure;

Complexes of 1,3-bis(2-thiazolylimino)isoindoline with middle and late first row transition metals by Goran Martić; James T. Engle; Christopher J. Ziegler (1749-1752).
In this communication, we present a study that probes the middle and late first row transition metal chemistry of 1,3-bis(2-thiazolylimino)isoindoline, adding to the known Fe and Cu compounds. Complexes of this ligand with Mn, Co, Zn and a new Fe form are presented and all are structurally characterized by single crystal X-ray methods. The 1,3-bis(2-thiazolylimino)isoindoline ligand can potentially bind via the thiazolyl nitrogen or sulfur atoms; in all of the complexes presented in this report, the N,N,N binding mode is observed exclusively. The ligands bind in a planar configuration, similar to that seen for bis(2-iminopyridyl)isoindoline.Herein, we present a study that probes the middle and late first row transition metal chemistry of 1,3 bis(thiazolylimino)isoindoline, adding to the known Fe and Cu compounds. Complexes of this ligand with Mn, Co, Zn, and a new Fe form are presented and are structurally characterized by X-ray methods.Display Omitted►The metal binding chemistry of 1,3-bis(2-thiazolylimino)isoindoline has been extended to new first row transition metal ions. ►The ligand chelates as a monoanion in the N,N,N binding mode. ►The X-ray structure of the free ligand as well as Mn, Fe, Co and Zn complexes is reported.
Keywords: Diiminoisoindoline; Bis(imimoaryl)isoindoline; Late and middle first row transition metal ions; Thiazole ligand; Homoleptic complexes;

Quantitative determination of the Lewis acidity of phenylboronic catechol esters — Promising anion receptors for polymer electrolytes by Agnieszka Adamczyk-Woźniak; Michał Jakubczyk; Andrzej Sporzyński; Grażyna Żukowska (1753-1755).
A series of catechol boronates were synthesized by esterification of the corresponding boronic acids. Lewis acidity of the obtained compounds was quantitatively evaluated by means of a modified Gutmann method. Introduction of the fluorine substituent into the phenyl ring resulted in increased Lewis acidity of the catechol esters. The highest effect was observed for the 2-fluoro derivative. No correlation of the AN was observed for the further increasing number of fluorine atoms, however the pentafluoro-substituted derivative was the strongest Lewis acids among studied. Its acidity is comparable to tris(pentafluorophenyl)borane, being considered one of the strongest organoboron acids. NMR-DFT calculations confirmed the relative trends in the Lewis acidity of compounds under study. It was found that the investigated complexation is reversible, which is crucial in both quantitative acceptor number determination as well as future applications of catechol boronates.Acceptor numbers (AN) of several boronic catechol esters are as high as those of the corresponding triphenylboranes. The complexation reaction with Et3PO is an equilibrium.Display Omitted► Acceptor numbers (ANs) of several boronic catechol esters have been determined. ► The AN values are as high as those of the strongly acidic triphenylboranes. ► The complexation with triphenylphosphine oxide was shown to be an equilibrium. ► The finding is crucial in AN determination as well as boronic esters applications.
Keywords: Boronic esters; Acceptor number; Polymer electrolytes; DFT-GIAO; NMR calculations;

Equilibrium characterization, magnetic susceptibility and fluorescence measurements proved that the silver(II) porphyrin complex formed in the reaction of the Ag+ ion and the 5,10,15,20-tetrakis(4-sulfonatophenyl)porphyrin ligand is of sitting-atop (SAT) type. The complex also exhibits typical SAT features as regards its photoredox degradation reactions, which might be utilized in photodynamic therapy. On the contrary, the corresponding gold(III) porphyrin is unambiguously of planar structure, which does not show any fluorescence and photoinduced degradation. The deviating structures, and hence, photoinduced behaviors of these complexes can be attributed to the effect of the different ionic radii (r ion(Ag2+) = 94 pm; r ion(Au3+) = 85 pm).Kinetically labile Ag(II)-5,10,15,20-tetrakis(4-sulfonatophenyl)porphyrin, deviating from the corresponding coplanar Au(III) complex, displays photophysical and photochemical behavior characteristic for metalloporphyrins of sitting-atop structure.Display Omitted► Reaction of Ag+ and H2TSPP4− gives a 1:1 silver(II) porphyrin complex. ► This compound of out-of-plane structure displays special photoinduced behavior. ► Its excitation leads to characteristic emission and an irreversible LMCT process. ► The smaller gold(III) ion (r Au3+  = 85 pm vs. r Ag2+  = 94 pm) forms in-plane AuIIITSPP3−. ► This complex, deviating from AgIITSPP4−, does not show any photoinduced activity.
Keywords: Porphyrin; Silver; Gold; Photochemistry; Sitting-atop features; Photodynamic therapy;

Photoluminescence studies on europium-based scorpionate-complex by Marco Bortoluzzi; Gino Paolucci; Stefano Polizzi; Luca Bellotto; Francesco Enrichi; Serena Ciorba; Bryce S. Richards (1762-1766).
The neutral homoleptic europium(III) complex Eu(Tp)3 (Tp = hydrotris(pyrazol-1-yl)borate) showed luminescence associated to f–f transitions if irradiated with near-ultraviolet radiation having wavelength lower than 380 nm. In this species the most intense emission corresponds to the 5D0  →  7  F4 transition, falling between 690 and 700 nm. The complex is stable towards oxygen, moisture and near-UV light. The energy levels of the coordinated ligands involved in the photoluminescence process were computed by applying computational methods and by carrying out luminescence measurements on the analogous Gd(III) complex.The Eu(III) complex Eu(Tp)3 (Tp = hydrotris(pyrazol-1-yl)borate) gives a metal-centred red emission associated to the 5D0  →  7FJ transitions if irradiated with near-ultraviolet light. This species is stable towards oxygen, moisture and UV light. The energy levels involved in the photoluminescence have been experimentally and theoretically investigated.Display Omitted► Eu(Tp)3 (Tp = hydrotris(pyrazol-1-yl)borate) is photoluminescent. ► The most intense emission corresponds to the 5D0  →  7  F4 f–f transition. ► The emission is caused by the absorption of near-UV radiation. ► The photostability of Eu(Tp)3 is good. ► Gd(Tp)3 emits in the blue-green region. ► The energy levels connected to luminescence have been investigated.
Keywords: Europium; Gadolinium; Photoluminescence; Scorpionates; PM6;

Influence of meridional N3-ligands on supramolecular assembling and redox behavior of carboxylatocopper(II) complexes by József S. Pap; Vanda Bányai; Dávid S. Szilvási; József Kaizer; Gábor Speier; Michel Giorgi (1767-1772).
Mononuclear phenylglyoxylato- and 4-R-benzoatocopper(II) complexes with two different 1,3-bis(2-arylimino)isoindoline ligands (aryl = pyridyl, or benzimidazolyl) have been synthesized and characterized. Coordination mode of the carboxylate ligands is very similar (monodentate) in each case, while redox behavior of the copper center is dependent on the aryl- and 4-R-substituents. The supramolecular assembly in the solid state via hydrogen bonds and π-stacking between the ligands can be influenced by the aryl-group and carboxylate ligand.H-bonded/p-stacked supramolecular assembling and redox properties are influenced in mononuclear carboxylatocopper(II) complexes with 1,3-bis(2-arylimino)isoindoline ligands.Display Omitted► Carboxylatocopper(II) complexes with isoindoline-based ligands synthesized. ► Redox properties of the Cu center can be controlled. ► Rich secondary interactions induce supramolecular assembling of the complexes.
Keywords: Copper(II); Isoindoline; Carboxylate; Redox chemistry; Supramolecular assembly;

Center-symmetric dimeric Re(CO)3 + complexes with Schiff base derivatives of salicylic aldehyde by Marek Grzegorczyk; Andrzej Kapturkiewicz; Jacek Nowacki; Agnieszka Trojanowska (1773-1776).
A simple synthetic procedure (reaction between Re(CO)5Cl and 2-[(E)-(phenylimino)methyl]- or 2-[(E)-(n-propylimino)-methyl]-phenol) leads to novel dimeric Re2(CO)6(N∩O)2 complexes with the structures confirmed by means of X-ray crystallography. The obtained species have been characterized by means of elemental analysis, FT-IR, UV–VIS absorption, and EI-MS spectroscopy. The solvolysis experiments performed in dimethylsulfoxide solutions point to well pronounced stability of the investigated species.A simple procedure (reaction in boiling toluene between Re(CO)5Cl and Schiff base ligands LH synthesized from salicylic aldehyde and alkyl or aryl amines) leads to novel center-symmetric dimeric complexes Re2(CO)6(L)2.Display Omitted► Schiff base derivatives of salicylic aldehyde LH react with Re(CO)5Cl with formation of dimeric species with general formula of Re(CO)6(L)2. ► The synthesized complexes have been characterized using EI-MS, UV-VIS, and IR spectroscopy. ► Centre-symmetric structures of the investigated complexes have been confirmed by means of X-ray investigations.
Keywords: Rhenium carbonyls; Schiff base ligands; X-ray crystallography; EI-MS; UV–VIS; IR spectroscopy;

Controlled hydrolysis of [Ti(O-2,4,6-Br3C6H2)2(O-iPr)2]2 with water results in the formation of the Ti-oxo cluster Ti8O24C66H58Br24 (1). This compound has a very interesting cage structure. The crystal structure consists of centrosymmetric neutral octamers containing two planar Ti4 layers, interlinked by four linear oxo-bridges. The four independent Ti atoms have three different coordination environments. The four unique Ti centers are rigidly coplanar, giving a unique configuration. The bridging oxygen atoms linking the two inversion-center related Ti atoms give a novel assemblage reminiscent of an inverse “cake-plate”. Compound 1 is an active initiator for the polymerization of cyclic ester monomers and lactide resulting in polymers with moderate number average molecular weights (M n) and close to narrow molecular weight distribution (MWD).Structure of a titanium cluster Ti8O24C66H58Br24 along with polymerization studies described.Display Omitted► Ti8O24C66H58Br24 has a cage structure. ► Ti centers are rigidly coplanar. ► Active initiator for the polymerization of cyclic esters and lactide.
Keywords: Ti-oxo cluster; ε-Caprolactone; δ-Valerolactone; L-Lactide; rac-Lactide;

Design and the cation-templated self-assembly on the [MoOS3Cu3]+ based supramolecular polymeric clusters by Zhen-Hua Zhang; Hong-Mei Wang; Yun-Yin Niu; Ben-Lai Wu; Seik-Weng Ng; Hong-Wei Hou (1783-1787).
Organic cation-templated self-assembly of 4,4′-bipy (4,4′-bipy = 4,4′-bipyridine) with [NH4]2MS2O2 (M = Mo, W) and CuX (X = I) in the presence of bppt [bppt = 1, 5-bis (pyridinium) pentane] resulted in two novel neutral heterothiometallic cluster polymers: {[Mo2O2S6Cu6BrI(4,4′-bipy)4] (4,4′-bipy)}n (1) and {[WOS3Cu3Br(4,4-bipy)2.5]·3 (DMF)}n (2). Compound 1 exhibits a neutral 3D 3-fold interpenetrating motif and compound 2 possesses a neutral 3D 4-fold interpenetrating architecture. Both of them have been characterized by IR, elemental analysis, TGA, UV–vis, PXRD, and single-crystal X-ray diffraction. The results may provide fascinating insights into the usage of template effect on the construction of the cluster-based coordination polymers.Organic cation-templated self-assembly of 4,4′-bipy (4,4′-bipy = bpy) with [NH4]2MS2O2 (M = Mo, W) and CuX (X = I) in the presence of bppt (bppt = 1, 5-bis (pyridinium) pentane) resulted in two novel neutral heterothiometallic cluster polymers: {[Mo2O2S6Cu6BrI(4,4′-bipy)4]. (4,4′-bipy)}n (1) and {[WOS3Cu3Br(4,4-bipy)2.5].3 (DMF)}n (2). Compound 1 is a neutral 3D 3-fold interpenetrating network and compound 2 is a neutral 3D 4-fold interpenetrating architecture. Both of them have been characterized by single-crystal X-ray diffraction, elemental analysis, PXRD, IR, TGA, and UV–vis. The results may provide fascinating insights into template effect on the construction of the cluster-based coordination polymers.Display Omitted► The first assembly of heterothiometallate with 1, ω-bolaamphiphile cation-template.► Compound 1 is a neutral 3-fold interpenetrating network. ► Compound 2 is a neutral 4-fold interpenetrating diamondoid network. ► The temporary cation template played a crucial role in building the polymers.
Keywords: Cation-template; Mo(W)–S–Cu clusters; Bppt; Interpenetrating net;

An extensive series of butyronitrile-substituted ruthenium chloride complexes [RuCl6 − nLn]z (n  = 0–6; L═CH3(CH2)2CN or PrCN) has been prepared and characterized spectro-electrochemically. The complete series allowed the examination of the variation in electrode potential of RuIII/II couple and the accompanying trends in both Cl → Ru(III) and Ru(II) → PrCN charge-transfer spectra. Systematic analysis of electrochemical and spectroscopic data led to a conceptual representation of the relative frontier-orbital energies of ruthenium, chloride, and nitrile as a function of stoichiometry.The preparation and spectro-electrochemical characterization of exhaustive series of butyronitrile-substituted ruthenium chloride complexes [RuCl6 − nLn]z (n  = 0–6; L═PrCN), allowed the examination of the variation in electrode potential of RuIII/II couple and the accompanying trends in both Cl → Ru(III) and Ru(II) → PrCN charge-transfer spectra.Display Omitted► A series of [RuCl6-nLn]z complexes has been characterized spectroelectrochemically. ► The RuIII/II redox potential varied linearly across the series. ► A non-additive ligand effect was notable in the truncated series n = 0, 1, trans-2. ► The Cl-to-Ru charge-transfer band moved irregularly across the series. ► •The notional redox potential for the halide and nitrile ligands drifted as well.
Keywords: Ruthenium complexes; Ligand effects; Electrode potentials; Charge-transfer spectra; Spectro-electrochemistry;

Two new heterometallic lanthanide(III)–natrium(I) coordination polymers [LnNa(4,4′-oba)(ox)(H2O)] (Ln = Nd 1, Sm 2) have been synthesized by hydrothermal reactions of 4,4′-Oxybis(benzoic acid) (4,4′-H2oba) and Na2C2O4 with corresponding lanthanide nitrate. Both compounds are isostructural and possess three-dimensional (3D) pillared-layer frameworks comprising Ln–Na-oxalate layers and 4,4′-oba pillars. The magnetic properties reveal that the two compounds have anti-ferromagnetic behaviors. Furthermore, the IR, PXRD, elemental and TG analyses are also investigated.Two isostructural 3D heterometallic lanthanide(III)–natrium(I) coordination polymers with pillared-layer frameworks assembled from Ln–Na-oxalate layers and 4,4′-oba pillars are reported. Both compounds show anti-ferromagnetic properties.Display Omitted► Two 3D heterometallic lanthanide(III)–natrium(I) coordination polymers with pillared-layer frameworks. ► Coordination frameworks assembled from Ln–Na-oxalate layers and 4,4′-oba pillars. ► Both compounds show anti-ferromagnetic properties.
Keywords: Lanthanide(III)–natrium(I); Pillared-layer frameworks; Hydrothermal reaction; Anti-ferromagnetic property;

An effective Hg2+-specific probe (1) was designed and prepared based on a rhodamine–nitrobenzoxadiazole conjugate. The sensing behavior of this probe was studied by UV–visible and fluorescence spectroscopy. With Hg2+, the probe displayed both colorimetric responses and ratiometric changes. The ratio of the absorption intensities at 525 and 460 nm for the two chromophores in the probe increased from 0.17 to 0.46. The probe exhibited excellent selectivity and sensitivity towards Hg2+ over other metal ions, which could be attributed to the Hg2+-triggered ring opening of the spirolactam of the rhodamine moiety and the formation of a 1:1 1-Hg2+ complex.Introduction of NBD fluorophore into rhodamine 6G contributes the “naked eye” detection for mercury and builds up a more precise method for monitoring Hg2+ by ratiometric measurement.Display Omitted► Monitoring the qualitative trends by ratiometric measurement. ► Detectable by using “naked eye” and fluorescence methods. ► It is easy to synthesize the probe 1.
Keywords: Mercury; Rhodamine; Nitrobenzoxadiazole; Colorimetric; Ratiometric;

A unique mixed-bridged trinuclear Co (II) complex and its extended system: Structural and magnetic studies by Yu-Ting Yang; Fang-Hua Zhao; Yun-Xia Che; Ji-Min Zheng (1802-1806).
Two novel complexes, [Co3(N3)2(bca)4(phen)2] (1, bca = benzenecarboxylic acid, phen = 1,10-Phenanthroline) and [Co3(N3)2(bdc)2(phen)2]n (2, bdc = terephthalic acid), have been synthesized hydrothermally and characterized by single crystal X-ray diffraction (XRD), infrared spectra (IR) and element analysis (EA). Complex 1 features unprecedented discrete linear Co3 clusters that formed by mixed (μ-EO-N3)(μ-COO)2 (EO = end-on) triple bridges whereas 2 presents an extended (2D) network based on the similar trinuclear units as 1. Magnetic studies of 1 and 2 reveal that the mixed (μ-EO-N3)(μ-COO)2 triple bridges transmit ferromagnetic behavior.Two novel complexes based on a linear trinuclear Co (II) unit with the mixed (μ-EO-N3)(μ-COO)2 triple bridges motif were synthesized under hydrothermal condition. Magnetic measurements show ferromagnetic coupling during linear Co3 units.Display Omitted► A unique mixed-bridged trinuclear Co3 cluster and its extended system. ► Linear trinuclear Co (II) unit with mixed triple bridges. ► Ferromagnetic coupling within [Co3(μ-EO-N3)2(μ-COO)4] trimer unit.
Keywords: Cobalt; Azide; Carboxylate; Mixed-bridges; Magnetic property;

Controllable assembly of organodisulfonate complexes with tuned mole ratios: From 0D to 3D networks by Wen-Jing Liu; Ning Wang; Zhi-Qiang Wei; Xia Zhao; Li-Mei Chang; Shan-Tang Yue; Ying-Liang Liu; Yue-Peng Cai (1807-1814).
Four novel organodisulfonate coordination polymers ranging from 0D cluster, 1D chain, 2D layer to 3D framework, {[Eu2(phen)4(nds)2(OH)2(H2O)2]·2H2O}n (1), {[Eu(phen)2(nds)0.5(OH)(H2O)]·0.5nds}n (2), {[Eu2(phen)4(nds)3(H2O)2]·7H2O}n (3), {Eu(phen)(nds)(OH)}n (4) (nds = 2,6-naphthanlenedisulfonate; phen = 1,10-phenanthroline), were synthesized by tuned stoichiometric ratio of the reactants and characterized by single crystal X-ray diffraction, elemental analysis, IR and thermogravimetric analysis. These complexes display a broad and strong ligand-centered luminescent emission band, and all of them have long luminescence lifetimes at millisecond order.Four novel organodisulfonate coordination polymers ranging from 0D cluster, 1D chain, 2D layer to 3D framework were synthesized by tuned stoichiometric ratio of the reactants and characterized by single crystal X-ray diffraction, elemental analysis, IR and thermogravimetric analysis, providing example of structure diversities exhibiting different luminescent properties through the same reactants.Display Omitted► Four novel organodisulfonate complexes have been synthesized. ► The only difference among four compositions is the stoichiometric ratio of the reactants. ► Structural diversities exhibit different luminescent properties.
Keywords: Lanthanide; Assembly; Organodisulfonate; Luminescence;

A highly twisting chiral qtz-d net built on a distorted tetrahedral node containing two types of helical substructure by Zhen-wei Liao; Hai-xiao Huang; Gong-ming Sun; Ming-biao Luo; Feng Luo (1815-1818).
Herein, we present one chiral metal-organic polymer, namely Cd2(μ-H2O)(L)2(4,4′-bpy)(1, 4,4′-bpy = 4,4′-bipyridine H2L = 2-(4-carboxyphenoxy)benzoic acid). The single crystal X-ray diffraction shows that polymer 1 crystallizes in the chiral P6 5 22 space group, and the overall structural feature is the intriguing topological building of twisting chrial qtz-d net bulit on a higly rare distorted tetrahedral node, containing two types of helical substructure.Herein, we present one chiral metal-organic polymer, namely Cd2(μ-H2O)(L)2(4,4′-bpy)(1, 4,4′-bpy = 4,4′-bipyridine H2L = 2-(4-carboxyphenoxy) benzoic acid). The single crystal X-ray diffraction shows that polymer 1 crystallizes in the chiral P6 5 22 space group, and the overall structural feature is the intriguing topological building of twisting chiral qtz-d net built on a highly rare distorted tetrahedral node, containing two types of helical substructure.Display Omitted► Presented here is a highly twisting qtz-d net. ► Cd2 unit is for the first time observed. ► It presents the first qtz-d net built on tetrahedral node.
Keywords: Hydrothermal synthesis; Chiral net; qtz-d net; Node;

A unique 3-D open coordination framework based on a fluorinated bis(imidazole) ligand has been prepared and characterized, showing a six-connected self-penetrating network with rob (48.66.8) topology. Porosity of desolvated and resolvated samples was characterized by X-ray powder diffraction (XRPD).A unique 3-D open metal-organic framework based on an fluorinated bis(imidazole) ligand has been prepared and characterized, showing a six-connected self-penetrating network with rob topology.Display Omitted► A novel fluorinated bis(imidazole) ligand is used to create 3D open framework ► The porous MnII coordination polymer has self-penetrating network with rob topology ► Thermal behavior and solid state fluorescent emissions are available
Keywords: Fluorinated bis(imidazole) ligands; MnII coordination polymer; Self-penetrating network; Rob topology;

The structural transformation from 2D layers to 3D nets by solvent-mediated cation-exchange reaction by Junhong Fu; Junxing Fu; Yajuan Mu; Yanhua Liu; Hongwei Hou; Yaoting Fan (1823-1826).
When metal–organic coordination polymers [M2(SO4)(TTTMB)2(H2O)4]·H2BTEC·2H2O (M = Cd: 1, Zn: 2; TTTMB = 1,3,5-tris(triazol-1-ylmethyl)-2,4,6-trimethylbenzene, H4BTEC = 1,2,4,5-benzenetetracarboxylate acid) with two dimensional layers were suspended in Cu(NO3)2 aqueous solution, a metal–organic coordination polymer [Cu2(TTTMB)(BTEC)(μ-H2O)(H2O)4]·6H2O (3) with three dimensional nets would be obtained by solvent-mediated cation-exchange reaction. The direct reaction of TTTMB and H4BTEC with CuSO4 in the absence of 1 or 2 affords different crystal [Cu3(TTTMB)2(H2BTEC)3(H2O)3]·3H2O (4).Through cation-exchange reaction, a Cd(II) or Zn(II) metal-organic coordination polymer with two dimensional layers can transform to a Cu(II) metal-organic coordination polymer with three dimensional nets. Visual evidence indicates that the reaction is a process of solvent-mediated reaction.Display Omitted► The structural transformation is from 2D Cd(II) or Zn(II) layers to 3D Cu(II) nets. ► The direct reaction of TTTMB and H4BTEC with CuSO4 affords a different crystal.
Keywords: Metal–organic coordination polymer; Solvent-mediated cation-exchange reaction; Structural transformation;

Spectral shifts upon core protonation of a series of electron-rich and electron-deficient porphyrins with five and six membered rings at the meso-positions have been studied by UV–vis and 1H NMR spectroscopy. The direction of the shift of the Q(0,0) band of different porphyrins depends on the electron-donating or electron-withdrawing character of the meso-substituent and therefore it may be used to evaluate the relative electron donor ability of the substituents. Also, the shift of the Soret bands was found to be influenced to a lesser extent by the electron donor ability of substituted groups at the porphyrin periphery. Although, large red shifts of the Soret band of H4T(o-NO2)P2+, H4T(p-SCH3P)P2+ and H4T(p-NO2P)P2+ indicate a significant out-of-plane deformation of porphyrin core, negligible upfield shifts of the β protons in their 1H NMR spectra show that the practice of using the change in the chemical shift of the β protons as an indicator of structurally induced changes in the porphyrin ring current should be approached with more caution. Interestingly, high level ab initio and DFT calculations demonstrate that in spite of the better electron donating ability of –OCH3 to benzene ring compared to that of –SCH3, meso-(p-SCH3)phenyl group is a clearly better electron donor to the porphyrin core than meso-(p-OCH3)phenyl one.Spectral shifts of a series of electron-rich and electron-deficient porphyrins bearing five and six membered rings at meso-positions upon core protonation with CF3COOH have been studied by UV-vis and 1H NMR spectroscopy. Stereoelectronic effects of the peripheral substituents on the position of the Soret and Q(0,0) bands of the dications as well as the shifts of the Hβ resonance have been discussed. High level ab initio and DFT calculations have been used to evaluate the relative electron donor ability of meso-PhSCH3 and meso-PhOCH3 groups to the diprotonated porphyrin core.Display Omitted► Shift of the Q(0,0) band as an evidence of the electron-rich or -deficient nature of porphyrins. ► meso-PhSCH3 as better electron donor to porphyrin core relative to meso-PhOCH3. ► Meso-substituents effects on the energy level of the a1u and a2u orbitals of porphyrin dications.
Keywords: Porphyrin dications; Nonplanar porphyrins; Soret band; Q(0,0) band; Ab initio and DFT calculations;

The organic macrocycle 5, 10, 15, 20-tetra-(p-hydroxy)phenylporphyrin (THPP), which is covalently bonded to inorganic silica networks, is used as the main sensitizer for synthesizing novel near-infrared (NIR) luminescent Ln-THPP-Si (Ln = Nd, Yb) hybrid materials. The structures and photophysical properties of obtained materials are studied in detail. Upon excitation at the maximum absorption of ligands, the resultant materials displayed characteristic near-infrared luminescence. These considerations show that interesting materials with potential applications in fluoroimmuno-assays, optical amplification and catalysis can be obtained.The organic macrocycle 5, 10, 15, 20-tetra-(p-hydroxy)phenylporphyrin (THPP), which is covalently bonded to inorganic silica networks, is used as the main sensitizer for synthesizing novel near-infrared (NIR) luminescent Ln-THPP-Si (Ln = Nd, Yb) hybrid materials.Display Omitted► Novel linkage of porphyrin derivative. ► Near-infrared luminescence. ► Novel kind of hybrid through coordination bonding.
Keywords: Lanthanide ion; Near-infrared luminescence; Porphyrins functionalized linkage; Chemically bonded hybrid materials;

Synthesis, structure, and catalytic activity of an organothorium hydride complex by Wenshan Ren; Ning Zhao; Liang Chen; Haibin Song; Guofu Zi (1838-1841).
Treatment of ThCl4(tmeda)2 with 3 equiv of [η 5-1,3-(Me3C)2C5H3]K in toluene under reflux gives the tris-Cp chloride complex [η 5-1,3-(Me3C)2C5H3]3ThCl (1) in 75% yield. The chlorine atom can be replaced by other groups via metathesis reactions. For example, reaction of 1 with an excess of KH in toluene under reflux affords the hydride complex [η 5-1,3-(Me3C)2C5H3]3ThH (2) in 68% yield. Complexes 1 and 2 have been characterized by various spectroscopic techniques, elemental analyses, and X-ray diffraction analyses. Complex 2 is an active catalyst for the polymerization of rac-lactide, leading to the atactic polylactides with high molecular weights and narrow molecular weight distributions.A new organothorium hydride complex has been prepared and structurally characterized. It is an active catalyst for the polymerization of rac-lactide, leading to the atactic polylactides.Display Omitted► A new organothorium hydride complex has been prepared and structurally characterized. ► It is an active catalyst for the polymerization of rac-lactide, leading to the atactic polylactides. ► The first example of the polymerization of lactide initiated by organoactinide complex has been reported.
Keywords: Thorium complex; Organothorium hydride; Polymerization of lactide;

A new layered germanate (C4N2H12)(NH4)2[(GeO2)3(GeO1.5F3)2] (denoted JLG-2) co-templated by diprotonated piperazine cations and ammonium ions has been solvothermally synthesized. JLG-2 was characterized by powder X-ray diffraction (XRD), inductively coupled plasma (ICP), and elemental (CHN). The structure was determined by single-crystal X-ray diffraction analysis. JLG-2 crystallizes in orthorhombic, space group Pbcn (No. 60), with a  = 7.1235(3) Å, b  = 11.7131(5) Å, c  = 20.9375(10) Å, and Z  = 4. The inorganic sheet of JLG-2 was built up from alternation of tetrahedral GeO4 and octahedral GeO3F3. Propeller-like chiral structure building units of Ge5O12F6 with Δ- and Λ-configuration were present in the inorganic sheet with a topology of 3, 9-net. The helical arrays of H-bonds formed between the arrays of diprotonated piperazine cations and the chiral chains that are built from the linkage of the propeller-like chiral SBUs with same configuration via O1, which was rare in pure germanate compounds.By employing the diprotonated piperazine cations and ammonium ions as the co-templates, a novel layered germanate (C4N2H12)(NH4)2[(GeO2)3(GeO1.5F3)2] (denoted JLG-2) has been synthesized under solvothermal condition. The inorganic sheet is alternatively linked by the chiral chains with opposite chirality, which is formed by the building units Ge5O12F6 with the same configuration. And helical arrays of hydrogen-bonds were formed by the interaction between the diprotonated piperazine cations and the monochiral inorganic chains.Display Omitted► A new layered germanate containing helical arrays of H-bond. ► The 3,9-net sheet was constructed by propeller-like SBUs with Δ- and Λ-configuration. ► The propeller-like SBUs with same configuration linked each other to form chiral chains.
Keywords: Chiral; Germanate; Helix; Hydrogen-bond; Solvothermal synthesis;

Supramolecular assembly based on Keggin cluster and basketlike cage by Kai Yu; Baibin Zhou; Yang Yu; Zhanhua Su; Chunmei Wang; Chunxiao Wang (1846-1849).
A novel supramolecular compound based on the Keggin cluster and basketlike cage (C10H10N2)12(PMoVI 12O40)2(Sr ⊂ P6Mo3 VMo15 VIO73)2·9H2O (1), has been hydrothermally synthesized and characterized by elemental analysis, IR, TG, XPS, UV and single-crystal X-ray diffraction. In compound 1, the basketlike polyanion uses its surface oxygen atoms to attract nine basket cages and five Keggin clusters via strong supramolecular interactions. Meanwhile, each of Keggin cluster is surrounded by its neighboring five basket cages in the same mode to form a 3D supramolecular framework with chambers, and 4,4′-bipy organic molecules are located in the chambers to stabilize the whole structure. The electrochemical and electrocatalysis behavior of 1-CPE have been studied in detail.A supramolecular compound based on the Keggin cluster and badsketlike cage (C10H10N2)12[(PMoVI 12O40)2(Sr ⊂ P6Mo3 VMo15 VIO73)2]·9H2O (1), is reported. The structure of compound 1 proves feasibility of the coexistence of two kinds of heteropolyanions in one compound. Electrochemical analysis shows that 1-CPE displays unique redox properties and good electrocatalytic activity to reduce nitrite.Display Omitted► A supramolecular compound based on the Keggin and badsketlike cage is reported. ► 1-CPE displays unique redox properties and electrocatalytic activity to nitrite. ► The work proves the feasibility of the coexistence of two kinds of POMs. ► Compound 1 provides prototype for design of compounds based on two kinds of POMs.
Keywords: Supramolecular assembly; Keggin cluster; Basketlike cage; Electrochemical property; Electrocatalysis behavior;