Inorganic Chemistry Communications (v.33, #C)

Contents List (iii-xiii).

A tetranuclear oxofluorovanadium(IV) cluster encapsulating a Na(H2O)n + subunit by Tiffany M. Smith; Nika Mahne; Andrey Prosvirin; Kim R. Dunbar; Jon Zubieta (1-5).
Hydrothermal reactions of sodium vanadate, methylenediphosphonic acid, hydrogen fluoride and the appropriate organoamine yielded the vanadium(IV)-oxyfluoride compounds [NH3(CH2)2(NH2)(CH2)2NH3]3[{Na(H2O)} ⊂ {V4O4F2(O3PCH2PO3)4}]·8H2O (1·8H2O) and [NH3(CH2)2(NH2)(CH2)2(NH2)(CH2)NH3]2[{Na(H2O)} ⊂ {V4HO4F2(O3PCH2PO3)4}]·7H2O (2·7H2O). The vanadium-oxyfluoride cationic unit {V4O4F2(O3PCH2PO3)4}10 − of the compounds consists of pairs of fluoride bridged {VFO5} octahedra linked through η4-diphosphonate ligands into a three polyhedra thick band. The {Na(H2O)n}+ groups occupy the interior of the band but are displaced from the centroid toward one face so as to project the aqua ligands into the extra-annular domain. The fluoride ligands bridge two vanadium sites as well as coordinating to the sodium cation.Hydrothermal syntheses provided oxofluorovanadium(IV) clusters encapsulating sodium cations: [{Na(H2O)n} ⊂ {V4O4F4(O3PCH2PO3)4}]10 − (n = 1 (1) and n = 2 (2)). A polyhedral/ball and stick representation of the cluster with n = 1 are shown.Display Omitted
Keywords: Oxofluorovanadium(IV) cluster; Vanadium-organophosphonate cluster; Sodium cation encapsulation; X-ray structure; Magnetic properties of vanadium(IV) tetranuclear clusters;

A fluorescent and colorimetric sensor for Al3 + based on a dibenzo-18-crown-6 derivative by Ya-Ping Li; Xiu-Ming Liu; Ying-Hui Zhang; Ze Chang (6-9).
A new receptor based on a dibenzo-18-crown-6 derivative is successfully synthesized and characterized. This receptor reveals selective recognition toward Al3 + ion, along with colorimetric and fluorometric dual-signaling responses based on internal charge transfer (ICT). Also, it can serve as a highly selective chemodosimeter for Al3 + with naked-eye detection.A new chemosensor based on 18-crown-6 derivative has been synthesized and characterized, which could serve as a ratiometric and colorimetric sensor for Al3 + based on internal charge transfer (ICT).Display Omitted
Keywords: Aluminum ion recognition; Dibenzo-18-crown-6 derivative; Ratiometric; Fluorescent; Chemosensor;

Two novel one-dimensional mercury selenidostannates with transition metal complexes: [Fe(phen)3]Hg2Sn2Se7·1.5eta·0.25H2O and [Ni2(teta)2(μ-teta)]HgSn3Se9 by Yu-Long Wang; Mei-Ling Feng; Kai-Yao Wang; Jian-Rong Li; Ze-Ping Wang; Guo-Dong Zou; Xiao-Ying Huang (10-14).
The compounds [Fe(phen)3]Hg2Sn2Se7·1.5eta·0.25H2O (phen = 1,10-phenanthroline; eta = ethanolamine) (1) and [Ni2(teta)2(μ-teta)]HgSn3Se9 (teta = triethylenetetramine) (2), have been synthesized under solvothermal conditions, which represent the first examples of mercury chalcogenidostannates incorporating transition metal (TM) complexes as counter cations and structure-directing agents. Compound 1 features a one-dimensional (1D) ribbon of [Hg2Sn2Se7] n 2n based on the {Hg2Sn2Se9} secondary building unit, whereas 2 features a 1D zigzag chain of [HgSn3Se9] n 4n assembled by the linkage of {HgSn3Se10} supertetrahedral T2 clusters. The optical absorption edges of 1 and 2 are estimated to be 1.88 and 2.29 eV, respectively. Thermal stabilities of 1 and 2 were investigated via thermogravimetric analyses.The first examples of mercury chalcogenidostannates with transition metal complexes as structure-directing agents, namely, [Fe(phen)3]Hg2Sn2Se7·1.5eta·0.25H2O (phen = 1,10-phenanthroline; eta = ethanolamine) (1) and [Ni2(teta)2(μ-teta)]HgSn3Se9 (teta = triethylenetetramine) (2), have been obtained solvothermally, whose structures feature different infinite chains.Display Omitted
Keywords: Mercury; Selenidostannates; Transition metal complex; Solvothermal synthesis; Crystal structure;

Two stacked 2Dchiral/2Dchiral  → 2Dachiral sheets based on V-shaped imidazolyl ligand and flexible aliphatic acids by Jin-Song Hu; Xin Zhuo; Xi-Hui Liu; Hong-Long Xing; Jie He; He-Gen Zheng (15-18).
Two new stacked 2Dchiral/2Dchiral  → 2Dachiral coordination polymers {[Cd(BIDPE)(pim)]·(H2O)}n (1) and {[Cd(BIDPE)(glu)]·(H2O)}n (2) were prepared under hydrothermal conditions based on V-shaped ligand 4,4′-bis(imidazol-1-yl)diphenyl ether (BIDPE) and flexible polycarboxylic acids. In addition, the solid-state photoluminescent spectra were measured at room temperature.Two new stacked 2Dchiral/2Dchiral  → 2Dachiral coordination polymers were synthesized based on V-shaped imidazolyl ligand and flexible polyaliphatic acids.Display Omitted
Keywords: Coordination polymer; V-Shaped ligand; Photoluminescent;

Based on two 2-substituted 8-hydroxyquinoline ligands containing ―NO2 and ―Cl, two complexes [Co(L2)2(pyridine)2] (1) and [Cu(L3)2] (2) were synthesized and characterized with single-crystal X-ray diffractions, powder X-ray diffractions (PXRD), thermal analyses (TGA) and elemental analyses (EA). In the solid state, the supramolecular structures of 1 and 2 feature two different two-folded helical chains, which were constructed by non-covalent interactions, such as π⋯π stacking, C―H⋯π, C―H⋯O, C―Cl⋯π and Cl⋯Cl interactions. The present research holds great promise in the development of novel functional helical structure, and may contribute to the understanding of helical organized systems in biology.Two complexes [Co(L1)2(pyridine)2] (1) and [Cu(L2)2] (2) were fabricated by self-assembly of M(II) ions with two novel 2-substituted-8-hydroxyquinoline ligands. The supramolecular structures of 1 and 2 feature two different two-folded helical chains and thereby 3D networks via non-covalent interactions.Display Omitted
Keywords: Assembly; Non-covalent interactions; Helical; 8-Hydroxyquinoline;

A 3-D lanthanide–organic framework based on in situ formed benzene-1,2,3,4-tetracarboxylate ligand by Jing-Yun Hu; Jiong Wen; Xiao-Gang Yang; Min Chen; Chun-Sen Liu (25-28).
One new 3-D open lanthanide–organic framework {[La2(L)1.5(H2O)4]∙2.75H2O} (1) (L  = benzene-1,2,3,4-tetracarboxylate) was synthesized and characterized by elemental analyses, IR spectrum, and single-crystal X-ray diffraction, respectively. Notably, 1,2-naphthalenedicarboxylic anhydride can be turned into benzene-1,2,3,4-tetracarboxylate (L) ligand upon an in situ reaction process under hydrothermal conditions. L ligand exhibited two different types of carboxyl coordination modes in 1, and bridged the lanthanum atoms to form a 2-D bilayer and then a 3-D open framework with (4,5,6)-connected (42.84) (32.44.52.62)4(32.45.53.64.7)2 topology. Moreover, luminescent properties of 1 have also been investigated.One new 3-D open lanthanide–organic framework {[La2(L)1.5(H2O)4]∙2.75H2O} (1) (L  = benzene-1,2,3,4-tetracarboxylate) has been hydrothermally synthesized through in situ ligand formation, which exhibited an unusual (4,5,6)-connected (42.84) (32.44.52.62)4(32.45.53.64.7)2 topology.Display Omitted
Keywords: Benzene-1,2,3,4-tetracarboxylic acid; Open framework; In situ reaction; Crystal/topology structures;

Two new metal–organic frameworks based on cyclic dodecanuclear copper units by Xiu-ping Zheng; Ying Lu; Huan Zhang; Zhi-ming Zhang; En-bo Wang (29-32).
Two new metal–organic frameworks based on cyclic-type dodecanuclear copper units, (Me4N)6[Cu12(OMe)6(pz)6(BTC)6]·18H2O 1 and (Me4N)6[Cu12(OH)6(pz)6(BTC)6]·21H2O 2 (pz = pyrazolate, BTC = 1,3,5-benzenetricarboxylate), have been prepared by the solvothermal reactions of copper salts, Hpz and H3BTC ligands. The cyclic-type Cu12 unit in 1 and 2 is constructed by twelve CuII ions linked together by μ2-OH or μ2-OMe and unidentate carboxylate groups at the inner- and μ-pz and bidentate carboxylate groups at the outer surface of the toroid. In 1 and 2, each Cu12 unit is connected to 12 other units by BTC linkers, leading to 12-connected three-dimensional porous frameworks. The photocatalytic investigations indicate that compounds 1 and 2 exhibit photocatalytic activity for the degradation of RhB.Two new 12-connected MOFs based on dodecanuclear copper units were synthesized and characterized.Display Omitted
Keywords: Metal–organic framework; Dodecanuclear copper unit; Cyclic-type unit; Structure; Photocatalytic activity;

Palladium(II) thiosemicarbazone-catalyzed Suzuki–Miyaura cross-coupling reactions of aryl halides by Devaraj Pandiarajan; Rengan Ramesh; Yu Liu; Rajamanickam Suresh (33-37).
A new air- and moisture-stable palladium(II) complex bearing pyridoxal thiosemicarbazone ligand has been synthesized. The synthesized complex was characterized by analytical and spectral methods. The molecular structure of the complex was confirmed by X-ray diffraction method. The palladium(II) complex was used as potential catalyst for Suzuki–Miyaura coupling reaction of several aryl halides under optimized conditions.New catalytically active palladium(II) thiosemicarbazone complex was synthesized and characterized. The single crystal X-ray analysis of the complex shows a typical square planar geometry around palladium(II) centre. The synthesized complex was successfully used as catalysts for Suzuki–Miyaura cross-coupling reaction.Display Omitted
Keywords: Palladium(II) pyridoxal thiosemicarbazone; Crystal structure; Suzuki–Miyaura cross-coupling reaction;

A new thick silver rod incorporating repeated Ag3 units sustained by 1,3,5-benzenetricarboxylic acid (1,3,5-H3BTC) and Ag⋯Ag interactions, {[Ag3(BTC)(pyz)]·(H2O)} n (1) (pyz = pyrazine), has been synthesized and structurally characterized. Compound 1 displays a three-dimensional coordination framework with infinite 1D Ag rod, and adjacent silver rods bridged by the 1,3,5-H3BTC and pyz ligand. Argentophilicity plays an important role in determining the infinite silver(I) rods. Complex 1 exhibits photoluminescence maximized at 542 nm upon 363 nm excitation at room temperature, which may be mainly assigned to ligand-to-metal charge transfer (LMCT) perturbed by Ag⋯Ag interactions. Temperature dependent luminescence spectra from 298 to 77 K have been studied. Upon decreasing the temperature from 298 to 77 K, the emission bands grow in intensity. In addition, the thermogravimetric analysis and powder X-ray diffraction (PXRD) of complex 1 have also been investigated.One new silver coordination polymer has been synthesized under solvent evaporation condition. This compound was characterized by X-ray single crystal diffraction, infrared spectroscopy, elemental analysis, and thermogravimetric analysis. In addition, temperature dependent luminescence spectra from 298 to 77 K have been studied.Display Omitted
Keywords: Coordination polymer; Silver rod; Ag⋯Ag interaction;

Interdigitated architectures assembled from α-metatungstates and lanthanide–organic complexes by Tingting Yu; Huiyuan Ma; Shaobin Li; Heng Liu; Haijun Pang (43-47).
Two new compounds were constructed by isopolyanions and lanthanide–organic units, [Hdpdo]Ln(Hdpdo)2(H2O)6[H2W12O40]·nH2O (Ln = Ce and n = 17 for 1, Ln = Nd and n = 18 for 2, dpdo = 4,4′-dipyridine-N,N′-dioxide) were synthesized at room temperature and characterized by IR and UV spectra, elemental analysis and single-crystal X-ray diffraction analysis. Compounds 1 and 2 are isostructural, and in their stacking architectures there exist poly-pendant wave-like layers formed by discrete {Ln(Hdpdo)2(H2O)6[H2W12O40]} fragments via ππ interactions, in which the [H2W12O40]6 − (W12) clusters as pendants are orderly appended to wave crests, by covalent bonds between Ln cations of Ln(Hdpdo)2 and terminal oxygen atoms of W12. Adjacent layers mutually engage in a zipper-like pattern to result in a novel 3D interdigitated architecture, in which overhanging W12 clusters act as teeth. Furthermore, the electrochemical studies show that 1 has a good electrocatalytic activity toward reduction of hydrogen peroxide (H2O2) molecules.Two new inorganic–organic hybrid compounds were synthesized, which represent the first examples of interdigitated architectures assembled from polyoxometalates and lanthanide–organic complexes.Display Omitted
Keywords: Polyoxometalate; Interdigitated; Lanthanide; Electrocatalytic activity;

A colorimetric and fluorescent chemosensor for selective detection of Cr3 + and Al3 + by Yeong Joon Jang; Yo Han Yeon; Hee Young Yang; Jin Young Noh; In Hong Hwang; Cheal Kim (48-51).
A chemosensor based on naphthol and quinoline moieties has been synthesized for the detection of Cr3 + and Al3 + as a colorimetric and fluorescent sensor in methanol. The sensor exhibited selective and sensitive recognition towards Cr3 + via color change from yellow to colorless. Moreover, it showed a significant fluorescence enhancement (50-fold) towards Al3 +.A chemosensor based on naphthol and quinoline moieties has been synthesized for the detection of Cr3 + and Al3 + as a colorimetric and fluorescent sensor in methanol. The sensor exhibited a selective colorimetric recognition towards Cr3 + via color change from yellow to colorless and a sensitive fluorescent recognition towards Al3 +.Display Omitted
Keywords: Chemosensor; Schiff-Base; Fluorescence; Colorimetric;

Two coordination polymers, {[(NiLallyl)2(BuTC)]∙2DEF∙2H2O} (1) and {[(NiLallyl)2(BuTC)]∙3H2O} (2), ([NiLallyl](ClO4)2  = [Ni(C14H30N6)](ClO4)2, H4BuTC = 1,2,3,4-butanetetracarboxylic acid, DEF =  N,N′-diethylformamide), were prepared by the self-assembly of [NiLallyl](ClO4)2 and H4BuTC in DEF/H2O and acetonitrile/H2O, respectively. Single crystal X-ray diffraction and X-ray powder diffraction (XRPD) results revealed that 1 and 2 have two-dimensional layered structures, and the layers were stacked infinitely. Further, guest molecules were intercalated between the layers. Since both of coordination polymers 1 and 2 were constructed from the same building blocks, the structure of each layer was identical. However, depending on the size and the nature of guest molecules, layer packing and the interlayer distances were different for each coordination polymer. Interestingly, due to the instability of DEF guest molecules intercalated in the coordination polymer 1, these guest molecules could be easily liberated from the host, consequently resulting in the same XRPD pattern as that of 2 with slightly different relative intensities. Dried compounds of 1 and 2 (1′ and 2′, respectively) also showed the same result as evidenced by the XRPD patterns. The similar but non-identical XRPD patterns were revealed that the dried structure 1′ had the same interlayer distance and the same intralayer structure as 2 and 2′ did, whereas its layer packing remained the same as that of 1. This subtle structural difference of 1′ and 2′ resulted in their different CO2 uptake behaviors at 195 K.We report the synthesis and single-crystal structures of two 2D coordination polymers, {[(NiLallyl)2(BuTC)]∙2DEF∙2H2O} (1) and {[(NiLallyl)2(BuTC)]∙3H2O} (2) (H4BuTC = 1,2,3,4-butanetetracarboxylic acid, [NiLallyl]2 +  = [Ni(C14H30N6)]) which are self-assembled in two different kinds of solvent systems, and their interesting structural flexibility and the CO2 sorption behavior depending on guest molecules.Display Omitted
Keywords: Coordination polymer; Structural flexibility; Guest dependency; Gas sorption; Self-assembly;

Template synthesis, structure and properties of 4-pyridinylboron-capped iron(II) clathrochelate precursors for Bubnov diallylation reaction by Ekaterina G. Lebed; Alexander S. Belov; Alexander V. Dolganov; Anna V. Vologzhanina; Valentin V. Novikov; Evgenii V. Kuznetsov; Yan Z. Voloshin (57-62).
Direct template macrobicyclization of three aliphatic, aromatic and dichlorine-containing a-dioxime molecules with 4-pyridinylboronic acid on a Fe2 + ion as a matrix afforded the first macrobicyclic tris-dioximates with 4-pyridinyl apical substituents. The macrobicyclic complexes synthesized were characterized using elemental analysis, spectroscopic methods, X-ray crystallography and cyclic voltammetry.First 4-pyridinylboron-capped iron(II) clathrochelates, which are prospective both the precursors for Bubnov diallylation reaction and the bridging ditopic N,N′-ligands for design of coordination polymers and polynuclear transition metal complexes, were obtained by template macrobicyclization of aliphatic, aromatic and halogenide α-dioximes with 4-pyridinylboronic acid on a Fe2 + ion as a matrix.Display Omitted
Keywords: Macrocyclic compounds; Clathrochelates; Iron complexes; Ligand reactivity; Allylation reactions;

A new asymmetric Schiff base system as fluorescent chemosensor for Al3 + ion by Reza Azadbakht; Tayebe Almasi; Hassan Keypour; Majid Rezaeivala (63-67).
A new fluorescent sensor, (E)-1-((2-((pyridin-2-ylmethyl)(2-(pyridin-2-ylmethylamino)ethyl)-amino)ethylimino)methyl) naphthalen-2-ol (HL), has been synthesized and characterized. Exhibiting absorption and fluorescence changes in the presence of Al3 + in ethanol solution, HL could be used as a colorimetric ‘naked eye’ and fluorescent chemosensor for the detection of Al3 + ions. The mechanism of fluorescence was based on the cation-induced inhibition of excited-state intramolecular proton transfer (ESIPT).A new asymmetric Schiff base chemosensor (HL) has been synthesized. HL possesses a high affinity and selectivity to Al3 + cations over 17 other metal cations by enhancement of the fluorescence emission. The sensor exhibits color change from pale yellow to colorless toward Al3 + ions.Display Omitted
Keywords: Chemosensors; Fluorescent probes; Naked-eye detection; Naphthalene; Aluminum ions;

Three bidentate pyrrolyl lithium complexes were synthesized and their application for the cyclotrimerization of isocyanate to corresponding isocyanurate has been investigated and show high catalytic activities. All lithium complexes were characterized by NMR spectroscopy, elemental analysis and X-ray diffraction analysis.A convenient and practical method for the cyclotrimerization of isocyanates is described. The reaction is catalyzed in the presence of catalytic amounts (0.1 mol%) of lithium compounds containing substituted pyrrolyl ligands leads to the corresponding isocyanurates in high yields (up to 98%).Display Omitted
Keywords: Lithium complex; Pyrrolyl; Cyclotrimerization; Isocyanate; Catalysis;

A new quaternary compound Ba3F2MnSe3 was synthesized by using a high-temperature solid-state reaction method in closed silica tubes at 1253 K. The compound displays an infinite one-dimensional corner-sharing MnSe3 tetragonal chain separated by 1D1 [Ba3F2]4 + cationic chains of the fluorite type. Magnetic susceptibility results verify the presence of the antiferromagnetic short-range order at low temperature.Ba3F2MnSe3 was synthesized by using a high-temperature solid-state reaction method in closed silica tubes, which is characterized by the existence of an infinite one-dimensional 1 [MnSe3]4 −upright chain constituted of corner-sharing, distorted MnSe4 tetrahedra. Magnetic susceptibility results verify the presence of a low-dimensional antiferromagnetic short-range order at low temperature.Display Omitted
Keywords: Crystal structure; Ba3F2MnSe3; MnSe3 chain; Short-range order;

The [IrCl5NO]− 1 ion in the potassium salt can be partially transformed into a metastable state by light irradiation in the violet-near UV region at low temperature (77 K). The excitation process was followed by infrared spectroscopy, comparing the spectra before and after irradiation.A new band grew at 1812 cm− 1 after irradiation with light in the 308–420 nm spectral region. The metastable state behavior is verified as this band decays upon heating the samples above 90 K or by subsequent irradiation using 450–680 nm light. The band at 1812 cm− 1 was assigned to ν(NO) of metastable state 1 (or an IrON linkage isomer) for comparison with the band position reported for other transition metal nitrosyls. To our knowledge, this is the first generation of a M-ON linkage isomer reported for a nitrosyl of transition metal of group 9. Its behavior is similar to that observed in other nitrosyl complexes of group 8.The [IrCl5NO]− 1 ion can be partially transformed into a metastable state (MS1) by light irradiation in the 308–420 nm spectral region at 77 K. The infrared band, that grew after irradiation at 1812 cm− 1, was assigned to ν(NO) of metastable state 1 (or an IrON linkage isomer).Display Omitted
Keywords: Metastable states; Low temperature infrared; Nitrosyl complexes; Iridium complexes; Photoexcited complexes; Linkage isomers;

Novel chiral coordination polymers, l-1 and d-1, with the formula [Cu4(OOCCH(OH)CH2COO)2] were synthesized through a reaction of copper acetate with l-malic acid and d-malic acid, respectively, in the presence of base under solvothermal condition. The X-ray crystallography for l-1 revealed that the copper centers of the complex were alternatively linked by a bis(oxygen) bridge and mixed bridge composing of oxygen and 1,3-carboxylate to construct a one-dimensional (1D) chain structure. These 1D chains interdigitated with each other to give a 3D polymer structure as a result of the coordination interaction linking the neighboring 1-D chain. The magnetic property was studied to show strong antiferromagnetic coupling (J/k  = − 596 K) within the chain and negligible one between the one-dimensional chain.Homochiral malic copper coordination polymer with 1-D magnetic structure was solvothermally obtained. The magnetic property was studied to show strong antiferromagnetic coupling (J  = − 596 K) within the chain and negligible one between the 1-D chain.Display Omitted
Keywords: Malic acid; Chiral complex; Crystal structure; Magnetic property;

Synthesis and characterization of novel gold(III) complexes with polydentate N-donor ligands based on the pyridine and triazole heterocycles by Marco Bortoluzzi; Alberto Scrivanti; Andrea Reolon; Emanuele Amadio; Valerio Bertolasi (82-85).
The coordination chemistry towards the Au(III) metal centre of the pyridine-triazole ligands 2-[(4-phenyl-1H-1,2,3-triazol-1-yl)methyl]pyridine (pytzPh ) and 2-[(4-pentyl-1H-1,2,3-triazol-1-yl)methyl]pyridine (pytzPent ) has been explored and complexes having formulae AuCl3(pytzPh) (1Ph ) and AuCl3(pytzPent) (1Pent ) have been isolated and characterised. Reaction of 1Ph with AgClO4 allowed the preparation of the compound [AuCl2(pytzPh)](ClO4) (2Ph ). Reaction of 1Ph and 1Pent with K[AuCl4]·2H2O led to the formation of the salts [HpytzPh][AuCl4] (3Ph ) and [HpytzPent][AuCl4] (3Pent ).The coordination chemistry towards Au(III) of pyridine-triazole ligands has been explored. These ligands form neutral and ionic mono-nuclear chloro-complexes. The coordination mode and the formation of the complexes appear strongly influenced by small changes of basicity caused by the introduction of alkyl- of aryl-substituents on the triazole moiety.Display Omitted
Keywords: Gold(III); Chloro-complexes; N-donor ligands; Pyridine; Triazole;

A new 3D [Co43-OH)2] cluster-based coordination framework, involving two different dicarboxylates ndc2 − and adc2 − along with secondary N-donor spacer bip, was prepared, which displays a rare 8-connected self-penetrating ilc net that can interestingly be regarded as the crosslink of two interpenetrating 6-connected pcu networks. In addition, the thermal stability and magnetic property of 1 were also investigated.A new 3D [Co43-OH)2] cluster-based coordination framework displays a rare 8-connected self-penetrating ilc net, which can interestingly be regarded as the crosslink of two interpenetrating 6-connected pcu networks.Display Omitted
Keywords: Co4-cluster network; Different dicarboxylates; Topology; Magnetic property;

Sandwich-type tungstoantimonates decorated by the heterometallic 3d–5p clusters by Hui Duan; Zhi-Ming Zhang; Xin-Bao Han; Yi-Zhen Chen; Jian-Qiang Shen; Wei-Peng Wang; Xiao-Tao Zheng; Huan-Yu Zhou; En-Bo Wang (90-94).
A new sandwich-type tungstoantimonate (NH4)9{Cu3Sb(H2O)3(SbW9O33)2}·22H2O (1) was synthesized by reaction of the preformed large cluster [NaSb9W21O86]18 − ({Sb9W21}) and transition-metal cations. Compound 1 is a 3d–5p heterometallic cluster-containing sandwich-type tungstoantimonate, which was further connected by the H-bonding interactions into a (4, 4)-connected two dimensional (2D) supramolecular framework. Further, the introduction of the alkali metal cations into the reaction system leads to a 2D framework based on the sandwich-type tungstoantimonate by water substitution: Na(NH4)9{SbCu3Cl(SbW9O33)2}·14H2O (2).A new 3d–5p heterometallic cluster-containing sandwich-type tungstoantimonate was synthesized by reaction of the preformed large cluster [NaSb9W21O86]18 − and transition-metal cations.Display Omitted
Keywords: Electrochemistry; Heterometallic cluster; Magnetism; Polyoxometalate; Sandwich;

A dimeric complex of [(tren)Ni(μ-Cl)2Ni(tren)](ClO4)2 (1) and a polymeric complex of {[Fe(CN)6][Ni(tren)]2[Ni(tren)(H2O)]2}Cl2(ClO4)2·4H2O (2), are isolated from the reaction of potassium ferricyanide, nickel chloride and tren and their X-ray structures and magnetic properties were characterized. Two [Ni(tren)]2 + units are linked through bis μ-Cl ligands forming dimeric structure of 1. In complex 2, there are two kinds of Ni(II) unit, terminal ([Ni(tren)(H2O)]2 +) and bridged ([Ni(tren)]2 +), and this bridged [Ni(tren)]2 + units are linked with two different Fe(II) ions through μ-NC ligands forming one-dimensional polymeric rectangular chain. 1 shows a weak ferromagnetic coupling between two Ni(II) ions and 2 shows spin crossover in Fe(II) ion.Dimeric complex 1 shows a weak ferromagnetic coupling and one-dimensional polymeric rectangular chain of complex 2 shows a spin crossover in Fe(II) ion.Display Omitted
Keywords: Tren; Ferrocyanide; Ni(II)2 dimer; Ferromagnetic coupling; Ni(II)4Fe(II) coordination polymer; Spin crossover;

A novel organic–inorganic hybrid sandwich-type germanotungstate [enH2]8[Fe4(en)(α-GeW9O34)2] [Fe4(en)2(α-GeW9O34)2]·en·14H2O has been synthesized by reaction of K8Na2[A-α-GeW9O34]·25 H2O, FeCl3, Ce(NH4)4(SO4)4·4H2O and en (en = ethylenediamine) under hydrothermal conditions and characterized by elemental analyses, IR spectrum, powder X-ray diffraction (PXRD), X-ray photoelectron spectroscopy (XPS) and single-crystal X-ray diffraction. To our knowledge, 1 represents the first organic–inorganic hybrid sandwich-type germanotungstate with discrete [Fe4(en)2(α-GeW9O34)2]8 − polyoxoanions and 1-D [Fe4(en)(α-GeW9O34)2]n 8n − polymeric chains in polyoxometalate chemistry. Thermogravimetric curve of 1 between 25 and 700 °C indicates two steps of weight loss. Variable-temperature magnetic susceptibilities of 1 exhibit the ferromagnetic interactions within the belt-like tetra-FeIII clusters mediated by the oxygen bridges.The first sandwich-type germanotungstate hybrid with discrete [Fe4(en)2(α-GeW9O34)2]8 − polyoxoanions and 1-D [Fe4(en)(α-GeW9O34)2]n 8n − polymeric chains has been synthesized, which exhibits the ferromagnetic interactions within the belt-like tetra-FeIII clusters.Display Omitted
Keywords: Polyoxometalate; Germanotungstate; 1-D sandwich-type germanotungstate;

Syntheses, structures and photoluminescence of two Dawson-based hybrid materials with polynuclear silver clusters by Zhenyu Shi; Jun Peng; Zheyu Zhang; Xia Yu; Kundawlet Alimaje; Xiang Wang (105-108).
Two new Dawson-based hybrids, namely, [Ag6(H L)4(H2O)6(P2W18O62)]·4H2O (1) and [Ag4(H2biim)4][K2(H2O)3(P2W18O62)]·H2O (2) (HL = 5-(4-imidazol-1-yl-phenyl)-2H-tetrazole, H2biim = 2,2′-biimidazole), have been hydrothermally synthesized and characterized. X-ray diffraction analysis reveals that compound 1 is a 3D structure based on infinite organic–metal chains {Ag6(HL)4}n and Wells–Dawson anions. Compound 2 displays a 3D framework based on potassium-Dawson inorganic sheets and dinuclear silver-H2biim units. The luminescent properties of compounds 1 and 2 have also been investigated.Two new POM-based hybrids (POM = polyoxometalate), namely, [Ag6(H L)4(H2O)6(P2W18O62)]·4H2O (1) and [Ag4(H2biim)4][K2(H2O)3(P2W18O62)]·H2O (2) (HL = 5-(4-imidazol-1-yl-phenyl)-2H-tetrazole, H2biim = 2,2′-biimidazole), have been hydrothermally synthesized and characterized. X-ray diffraction analysis reveals that compound 1 is a 3D structure based on infinite organic-metal chains {Ag6(HL)4}n and Wells–Dawson anions. Compound 2 displays a 3D framework based on potassium-POM inorganic sheets and dinuclear silver-H2biim units.Display Omitted
Keywords: Dawson; Hydrothermal synthesis; Hybrid; Polynuclear;

Molecular conductors with anti-7,7′:8,8′-bis(dithio)bis(7,8-dicarbaundecaborate) anion by Andrey V. Kravchenko; Sergey V. Timofeev; Olga N. Kazheva; Grigorii G. Alexandrov; Igor B. Sivaev; Vladimir I. Bregadze; Vladimir A. Starodub; Lev I. Buravov; Oleg A. Dyachenko (109-113).
New radical cation salts (BEDT-TTF)2[anti-7,7′:8,8′-bis(dithio)bis(7,8-dicarba-undecaborate)] and (TMTTF)2[anti-7,7′:8,8′-bis(dithio)bis(7,8-dicarbaundecaborate)] were obtained by electrocrystallization from solution of bis(ortho-carboranyl-1,2-dithiolate)cobalt(II) complex (Me4N)2[Co(1,2-S2C2B10H10)2] and BEDT-TTF or TMTTF, respectively, in acetonitrile – 1,1,2-thrichloroethane. The process is accompanied with the complex demetallation, partial deboronation of the carborane cage and oxidation of dithiolate to cyclic bis(disulfide). X-ray crystal structures and electrical conductivities of the compounds synthesized were determined.New radical cation salts (BEDT-TTF)2[anti-7,7′:8,8′-bis(dithio)bis(7,8-dicarbaundecaborate)] and (TMTTF)2[anti-7,7′:8,8′-bis(dithio)bis(7,8-dicarbaundecaborate)] were obtained by electrocrystallization from solution of bis(ortho-carboranyl-1,2-dithiolate)cobalt(II) complex (Me4N)2[Co(1,2-S2C2B10H10)2] and the corresponding tetrathiafulvalene derivatives.Display Omitted
Keywords: Carborane; Bis(ethylenedithio)tetrathiafulvalene; Tetramethyltetrathiafulvalene; Cation radical salts; Crystal structure; Electric conductivity;

Reversible photoluminescence switch: A stair-step Cu4I4 coordination polymer based on a dithioether ligand by Tae Ho Kim; Sangjin Lee; Youngeun Jeon; Yong Woon Shin; Jineun Kim (114-117).
A two-dimensional network stair-step Cu4I4 coordination polymer (1) based on 1,4-bis((methylthio)propanoyl)piperazine was prepared. No emission was observed from 1 (off state), while a heated sample (2) of 1 emitted a strong green light (on state). Conversion between 1 and 2 was reversible upon removal of acetonitrile or exposure of 2 to acetonitrile.Presented here are Cu(I) coordination polymers exhibiting reversible luminescence switching on/off property upon removal and exposure of acetonitrile.Display Omitted
Keywords: Copper(I) iodide; Luminescence switch; Coordination polymer; Dithioether ligand; VOC;

A new copper(II) complex Cu(II)-L containing N2O2 donor atoms has been prepared from 6-[3′-(N-pyrrol)propoxy]-2-hydroxyacetophenone and diaminoethane in the presence of copper acetate monohydrate. It was characterized by spectroscopic methods such as FT-IR, UV–vis, mass spectra, elemental analysis and cyclic voltammetry. The molecular structure of Cu(II)-L has also been confirmed by X-ray diffraction analysis. The electrochemical behavior of copper(II)-Schiff base complex containing pyrrol groups has been investigated in DMF and acetonitrile solutions using cyclic voltammetry. Thus, conducting polymeric films of polypyrrole were obtained on the surfaces of glassy carbon and ITO electrodes using copper(II) complex as monomer. The modified electrodes were electrochemically and morphologically characterized and their electrocatalytic properties in heterogeneous phase have also been investigated. The AFM studies show that the morphology of polypyrrole (PPy) films on ITO-electrodes depends on the number of cyclical scans. The electrocatalytic performances of this complex seem to be more efficient towards the electro-oxidation of isopropylic alcohol than any other kinds of alcohols such as methanol, ethanol and benzyl alcohol. The electro-reduction of carbon dioxide was also examined.Display Omitted
Keywords: Copper(II)-Schiff base complex; Pyrrolic monomers; Modified electrodes; X-ray diffraction; Oxidation of aliphatic alcohols;

Synthesis and characterization of a dipyridocatecholate silicon complex by David A. Lee; Sang K. Moon; Adrian N. Sizeland; Nicholas W. Gould; Eshere M. Gbarbea; Deborah Owusu; Daniel S. Jones; Thomas A. Schmedake (125-128).
The reaction of [Si(bpy)2I2]I2 with 1,10-phenanthroline-5,6-dione followed by metathesis provides various salts of [Si(bpy)2(dpcat)]+ 2 (1, bpy = 2,2′-bipyridine and dpcat = dipyridocatecholate). Recrystallization of [Si(bpy)2(dpcat)](ClO4)2 from an aqueous solution of NaClO4 afforded orange crystals of Na[Si(bpy)2(dpcatH)](ClO4)4·3H2O (2), in which silicon possesses a distorted octahedral geometry. The dipyridocatecholate ligand is coordinated to the silicon through the oxygen atoms, and one of the nitrogen atoms is protonated. 29Si NMR and ESI-mass spectroscopy indicate [Si(bpy)2(dpcat)]+ 2 maintains its hexacoordinate structure in solution. The complex is stable with respect to hydrolysis, and degassed aqueous solutions luminesce at 410 nm.The reaction of [Si(bpy)2I2]I2 with 1,10-phenanthroline-5,6-dione followed by metathesis provides salts of [Si(bpy)2(dpcat)]+2 (1, bpy = 2,2′-bipyridine and dpcat = dipyridocatecholate). Recrystallization of [Si(bpy)2(dpcat)](ClO4)2 from an aqueous solution of NaClO4 afforded orange crystals of Na[Si(bpy)2(H-dpcat)](ClO4)4·3H2O (2), in which silicon possessed a distorted octahedral geometry.Display Omitted
Keywords: Hexacoordinate silicon; Polypyridine; 29Si NMR; 1,10-Phenanthroline-5,6-dione; Dipyridocatecholate;

Manganese(II)-promoted ligand oxidation during the formation of a coordination polymer by Zhao Su; Qi Yue; Xiu-Chun Yi; Kun Wang; En-Qing Gao (129-132).
During the synthesis of Mn(II) compounds from fluorene-2,7-dicarboxylate, the ligand undergoes in situ oxidation to generate a Mn(II) coordination polymer with the ligand fluorenone-2,7-dicarboxylate (FODC2 −). It was demonstrated that the transformation occurs with dioxygen as reactant and Mn(II) as catalyst. The resulting coordination polymer, [Mn3(FODC)3(DMA)4]⋅2.5DMA, displays a 2D network based on the [Mn3(COO)6(DMA)4] unit with triple carboxylate bridges. Magnetic analyses were performed not only on temperature-variable susceptibility but also on field-variable magnetization, indicating weak antiferromagnetic interactions through the triple bridges.When reacting with Mn(II), fluorene-2,7-dicarboxylic acid undergoes in situ oxidation to generate a two-dimensional coordination polymer with fluorenone-2,7-dicarboxylate, which is based on trinuclear units and displays antiferromagnetic exchange.Display Omitted
Keywords: Carboxylate; Coordination polymer; In situ oxidation; Magnetic properties; Manganese;

Structural, magnetic, and 1H NMR spectral study on lantern-type cis- and trans-diruthenium(II,III) complexes with two formamidinato and two acetato bridges by Takahisa Ikeue; Yuko Kimura; Kazuhiro Karino; Masanari Iida; Tomoe Yamaji; Ichiro Hiromitsu; Tamotsu Sugimori; Daisuke Yoshioka; Masahiro Mikuriya; Makoto Handa (133-137).
Lantern-type dinuclear complexes, cis-[Ru2(4-Me-pf)2(O2CMe)2Cl] and trans-[Ru2(2,6-Et2-pf)2(O2CMe)2Cl] (4-Me-pf  =  N,N′-bis(4-methylphenyl)formamidinate ion and 2,6-Et2-pf  =  N,N′-bis(2,6-diethylphenyl)formamidinate ion), were prepared and characterized. The dinuclear structures with cis- and trans-arrangements of the bridging ligands were confirmed by the X-ray crystal structures as well as 1H NMR spectra (298 K) in CD2Cl2, where the proton signals were observed at widely spread positions δ = − 80 to 25 ppm. Variable-temperature magnetic moments (2–300 K) showed the existence of three unpaired electrons in dinuclear units with large D values (65 cm− 1 for cis-Ru2 II,III and 90 cm− 1 for trans-Ru2 II,III).The paramagnetic lantern-type dinuclear complexes, cis-[Ru2(4-Me-pf)2(O2CMe)2Cl] and trans-[Ru2(2,6-Et2-pf)2(O2CMe)2Cl] were prepared and characterized. The cis- and trans-(2:2) arrangements of the bridging ligands were confirmed by X-ray crystal structures and 1H NMR spectra (298 K) in CD2Cl2.Display Omitted
Keywords: Diruthenium(II,III); Formamidinato and acetato bridges; Cis- and trans-(2:2) arrangements; Crystal structures; Magnetism; 1H NMR;

X-ray single-crystal structure and magnetic properties of KMn(H2O)5Ru2(CO3)4·5H2O: A layered soft magnet by Dan Wang; Bin Liu; Jin Jin; Xue-Mei Liu; Yan-Yan Jia; Gang-Lin Xue (138-141).
The temperature manipulation induces the aggregation of Ru2(CO3)4 3 − paddle-wheel precursors and Mn2 + ions in lower temperature ~ 10 °C forming layer structural complex, K[Mn(H2O)4Ru2(CO3)4]·5H2O (1). It composes of new negative layer {Mn(H2O)5Ru2(CO3)4} n n, and magnetic exchanges between spin centers result in ordering below 3.8 K. The observed critical temperature is like the previously reported 3D hetero-metallic carbonates H0.3K0.7Mn[Ru2(CO3)4](H2O)5.5, which demonstrates that it is independent of the interlayer connecting in such heterometallic complexes based on square-grid layer {Ru2(CO3)4} n 3n.The temperature manipulation induces the aggregation of Ru2(CO3)4 3 − paddle-wheel precursors and Mn2 + cations in lower temperature ~ 10 °C forming layer structural soft magnet, KMn(H2O)4Ru2(CO3)4  · 5H2O (1), showing T c  = 3.8 K.Display Omitted
Keywords: Heterometallic; Diruthenium; Manganese; Structure; Magnetism;

Two novel complexes [H2N(CH2CH2)2O]4[Na(H2O)2{O(CH2CH2)2NH2}]2[Na(H2O)4]2[V10O28][NiMo6O24H6]·8H2O (1) and [H2N(CH2CH2)2O]6[Na(H2O)3]2[V10O28H2][NiMo6O24H6]·4H2O (2) containing both isopolyvanadate {V10O28} and [NiMo6O24H6]4 − units have been synthesized and structurally characterized for the first time, showing that the pH value of the reaction plays a key role in structure control of self-assembled processes. Compound 1 exhibits a novel one-dimensional (1-D) chain-like structure consisting of Anderson-type [NiMo6O24H6]4 − and isopolyvanadate [V10O28]6 − anions linked by Na+ ions. In compound 2 with the lower pH value, [NiMo6O24H6]4 − and [V10O28H2]4 − anions are bridged by [Na2O10] units to form the 2D extended layer. The magnetic properties of 1 and 2 are presented.Two novel complexes consisting of both {V10O28} and [NiMo6O24H6]4 − units arise from a pH-dependent self-assembly process, in which both {V10O28} and [NiMo6O24H6]4 − anions could be bridged by Na+ ions to form the 1D chain-like and 2D layer structures under lower pH value.Display Omitted
Keywords: Polyoxometalate; Crystal structure; Anderson-type polyanions; Isopolyvanadate; Sodium ions;

First example of perfluoroalkylation of a quasi-aromatic encapsulating ligand: 2,5-Dithiahexane-assisted reaction of the iron(II) diiodoclathrochelate with trifluoromethylcopper(I) by Oleg A. Varzatskii; Irina N. Denisenko; Sergey V. Volkov; Alexander V. Dolganov; Anna V. Vologzhanina; Yurii N. Bubnov; Yan Z. Voloshin (147-150).
Perfluoroalkylation of an iron(II) diiodoclathrochelate precursor with trifluoromethyltrimethylsilane and copper(I) iodide in THF using 2,5-dithiahexane as a co-ligand and potassium fluoride as the base afforded mono- and bis-trifluoromethylated cage complexes in moderate yields. These complexes were characterized using elemental analysis, MALDI-TOF mass spectrometry, IR, UV–Vis, 1H, 11B, 19F and 13C{1H} NMR spectroscopies, and by X-ray crystallography. The geometry of their FeN6-coordination polyhedra is intermediate between a trigonal prism and a trigonal antiprism, the encapsulated iron(II) ions are located almost in the center of these polyhedra. The average Fe–N distances (av. 1.91 Å), the distortion φ angles (approximately 26°) and the heights h of the coordination polyhedra (2.31 Å) are characteristic of the boron-capped iron(II) clathrochelates. The anodic ranges of the cyclic voltammograms for the trifluoromethylated iron(II) clathrochelates contain one-electron waves of an irreversible oxidation assigned to the metal-centered redox process Fe2 +/3 +, while those in their cathodic ranges were assigned to the Fe2 +/+ reduction. The ribbed functionalization of the iron clathrochelates with trifluoromethyl substituent(s) destabilizes both their oxidized and reduced forms.The perfluoroalkylation of iron(II) diiodoclathrochelate precursor with (CF3)Cu afforded mono- and bis-trifluoromethylated cage complexes in moderate yields, which were characterized using spectral methods and X-ray diffraction. According to cyclic voltammetry data, the ribbed functionalization of the iron clathrochelates with trifluoromethyl substituent(s) destabilizes both their oxidized and reduced forms.Display Omitted
Keywords: Macrocyclic compounds; Clathrochelates; Iron complexes; Ligand reactivity; Copper-promoted reactions; Fluorine compounds;

Enhanced oxide ion conductivity in stabilized cubic BaInO2.5 by Mn5 + doping by Yuzeng Sun; Chengxu Yang; Ting Shu; Guobao Li; Fuhui Liao; Jianhua Lin (151-153).
The preparation of room-temperature stabilized cubic BaInO2.5 was successfully achieved by adjusting Mn5 + doping (0.13 ≤ x ≤ 0.33) using high-temperature solid state reactions. XPS and magnetic investigations revealed that the valence state of Mn ions in stabilized cubic BaInO2.5 was + 5. The stabilized cubic BaInO2.5 showed enhanced oxide ion conductivity, and the best low-temperature conductivity at 400 °C was 3.0 × 10− 3  S cm− 1, which was larger than previously reported highest conductivity for stabilized cubic BaInO2.5.By doping Mn5 + on the In site, the cubic cell of BaInO2.5 was stabilized to room temperature with enhanced conductivity.Display Omitted
Keywords: BaInO2.5; Mn5 + doping; Enhanced oxide ion conductivity;

Synthesis, characterization and preliminary in vitro cellular uptake studies of 67Ga(III) thiosemicarbazones by Tawfeeq Ismail; Daniel D. Rossouw; Philip Beukes; Jacobus P. Slabbert; Gregory S. Smith (154-157).
Preliminary experiments were conducted using the radiometal 67Ga and a select series of thiosemicarbazones. A series of five monothiosemicarbazone ligands was synthesized via a Schiff-base condensation reaction. Radiolabelling studies were performed using 67GaCl3. The successfully radiolabelled complexes (with labelling efficiencies ranging from 87% to more than 99%) were tested for their radiochemical stability in saline and foetal bovine serum. While all the complexes are stable in saline, only one compound showed some degree of radiochemical stability in serum. In vitro cellular uptake of the radiochemically stable complex was evaluated against rat ovarian cancer (DMBA OC1R) cells, human breast cancer (MCF 7) cells and non-cancerous brain endothelial (bEND5) cells. A clear correlation between cellular uptake of the radiolabelled complex and cell count was observed.Five monothiosemicarbazone ligands were labelled using the radiometal 67Ga. All the complexes are stable in saline, however, only one showed radiochemical stability in serum.Display Omitted
Keywords: Thiosemicarbazones; 67Gallium; Stability studies; In vitro cellular uptake;

A tetrazolate-based coordination complex with novel 3D structure and catalytic property by Pei-Jiang Liu; Dong-Sheng Ma; Dan Xiao; Guang-Feng Hou (158-160).
Hydrothermal reaction of 5-(4-nitrophenyl)-2H-tetrazole [H(4-nptz)] and CuCl generates a novel complex Cu(4-nptz). In complex (1), the tetrahedral Cu(I) cations are linked by μ4-4-nptz ligands into a 4-connected 3D framework with sra topology. Complex (1) represents the first 3D structure constructed by 4-nptz ligand, and it is insolvable in all solutions and stable in room temperature. However, it will explode when the temperature is higher than 360 °C. UV–vis diffuse reflectance spectroscopy (DRS) of complex (1) exhibits a strong absorption band in the visible light region around 750 nm. In addition, complex (1) exhibits catalytic property to the hydrolysis of ester.A tetrazole–Cu(I) complex is hydrothermal synthesized with interesting 3D sra type framework and catalytic properties to the hydrolysis of ester.Display Omitted
Keywords: Metal–organic framework; Tetrazole; Crystal structure; Catalysis;

The reaction of 1-(chloromethyl)-4-aza-1-azonia-bicyclo[2.2.2]octane chloride and divalent metal copper chloride in dilute hydrochloric acid and perchloric acid mediums yields two five-coordinate copper (II) complexes, C7H16Cl4CuN2O (1) with trigonal–bipyramidal geometry and C14H28Cl6CuN4O8 (2) with novel square–pyramidal geometry respectively. Their crystal structures have been determined by X-ray crystallography at room temperature and low temperature. Dielectric constants of these two complexes increase with increasing temperature and decrease with increasing frequency when measured at different temperatures and frequencies. The complex 2 is more sensitive to diverse frequencies than complex 1 and also shows dielectric anomaly and corresponding dielectric loss behavior at 173 K as the result of the disorder–order transition of perchlorate anions.Two novel five-coordinate metal–organic–inorganic complexes Cu(LCH2Cl)Cl3H2O (1) and [Cu(LCH2Cl)2Cl2](ClO4)2 (2) (L+CH2Cl = N-chloromethyl-1,4-diazabicyclo[2.2.2]octonium ion) were prepared with two different geometries. Compound 1 displays 1D chain structure cross-linked by hydrogen bonds, compound 2 displays 0D layer structure with disorder–order transition of ClO4 anions at different temperatures. Different structures lead to large discrepancy in the frequency and temperature dependence of the dielectric constant measurements.Display Omitted
Keywords: Five-coordinate; Structure; Dielectric constant; Temperature; Frequency;

A facile way to synthesis KMgF3 and its luminescent property with Eu doping by Wei Wang; Xiaoyang Liu; Jingchao Zhang; Ying Ji; Nan Jiang; Bing Ma; Xiaofeng Wang; Li Liu (165-169).
KMgF3 and KMgF3: Eu samples were firstly fabricated by molten salt synthesis (MSS) method in NH4HF2 flux without any surfactants. The NH4HF2 flux was utilized as both the reactant and the fluxing agent. The products with uniform and regular morphologies were characterized by X-ray diffraction (XRD), thermal stability (TG), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and photoluminescence (PL) spectra. The luminescent properties show that the obtained KMgF3 sample got a broad band blue emission at about 430 nm arising from the trace oxygen and the color center, and the KMgF3: Eu sample exhibited fantastic emission under the excitation of different wavelengths.Emssion spectra of the Eu-doped KMgF3 sample. The emission spectrum of the KMgF3 microcrystal, which was excited at 261–371 nm and at 352–382 nm.Display Omitted
Keywords: KMgF3; Molten salt synthesis; Luminescence;

Based on a highly flexible H2L (2,2′-thiodiacetic acid) ligand and corresponding lead(II) salts, a series of novel lead(II) inorganic–organic hybrid frameworks {[Pb26-L)(μ7-L)]}n (1), [Pb(μ6-L)]n (2) and {Pb38-L)22-Cl)2}n (3) have been isolated under hydrothermal conditions. 1 and 2 represent a novel example of tuning the inorganic–organic hybrid frameworks from I1O1 type to I2O0 type and coordination geometries of lead(II) via changing the hydrothermal reaction temperature. When halide chloride anions were introduced into the reaction system, another novel hybrid framework 3 can be isolated. In 3, 1D infinite Pb–O–Pb and Pb–Cl–Pb connectivity can be observed, which are inter-linked forming another type of 2D inorganic–organic framework with I2O0 type. Four different coordination modes of full de-protonated L2 − ligand can be observed in 13. The variable lead(II) geometries and coordination numbers together with flexible coordination modes of de-protonated L2 − ligand also reveal great potential in the rational design and deliberate construction of those novel inorganic–organic hybrid materials.A series of novel lead(II) inorganic-organic hybrid frameworks have been isolated under hydrothermal conditions. The variable lead(II) geometries and coordination numbers together with flexible coordination modes of de-protonated L2 − ligand also reveal great potential in the rational design and deliberate construction of those novel inorganic-organic hybrid materials.Display Omitted
Keywords: Hybrid frameworks; Reaction temperature; Halide anions;