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An organic-inorganic hybrid polyiodate, namely, [o-C5 H4 NHOH]2 [I7 O18 (OH)]⋅3 H2 O (I), featuring a novel branched polyiodate chain has been obtained by evaporation method. [o-C5 H4 NHOH]2 [I7 O18 (OH)]⋅3 H2 O (I) crystalizes in the polar space group Ia and features an [I7 O18 (OH)] ∞2- branched polyiodate chain in which [I3 O9 ]3- trimers are grafted on the same side of the one-dimensional (1D) chain based on [I4 O11 (OH)]3- tetramers. The asymmetric organic amine groups are beneficial to the polymerization of iodate groups and inducing the formation of the non-centrosymmetric (NCS) structure. Compound I exhibits a rather large Second-Harmonic- Generation (SHG) signal of 8.5×KH2 PO4 (KDP) upon 1064 nm laser radiation, a moderate band gap of 3.90 eV and a high laser-induced-damage-threshold (LIDT) of 182.34 MW cm-2 , hence it is a promising new SHG material. The relationship between the structures of the organic amine groups and the overall structures has been also analyzed.

The first alkali-metal vanadium iodate fluoride, CsVO2 F(IO3 ), with a novel 3D anionic framework, has been rationally designed and hydrothermally synthesized. The 3D [VO2 F(IO3 )]- framework in CsVO2 F(IO3 ) is built from 0D Λ-shaped cis-[VO3 F(IO3 )2 ]4- polyanions via corner-sharing of oxo anions and bridging of the iodate groups. CsVO2 F(IO3 ) displays both a strong second-harmonic generation (SHG) 1.1 times as strong as KTiOPO4 (KTP) under 2.05 μm laser radiation and high laser-induced damage threshold (LIDT) of 107.9 MW cm-2 . This work provides a new route to design SHG crystals with stable 3D anionic structures from low-dimensional structural building units.

Through systematic experiments, two novel mercury iodate sulfates, namely, Hg

In response to ever-increasing application requirements in lighting and displays, a tremendous emphasis is being placed on single-component white-light emission. Single-component inorganic borates doped with rare earth metal ions have shown prominent achievements in white-light emission. The first environmentally friendly defect-induced white-light emitting crystalline inorganic borate, Ba2 [Sn(OH)6 ][B(OH)4 ]2 , has been prepared. Additionally, it is the first borate-stannate without a Sn-O-B linkage. Notably, Ba2 [Sn(OH)6 ][B(OH)4 ]2 shows Commission Internationale de l'Eclairage (CIE) chromaticity coordinates of (0.42, 0.38), an ultrahigh color rendering index (CRI) of 94.1, and an appropriate correlated color temperature (CCT) of 3083 K. Such a promising material will provide a new approach in the development of white-light emitting applications.

A cesium bismuth germanate, Cs2Bi2O(Ge2O7) (CBGO), was synthesized by a traditional high-temperature solid-state reaction. Its structure features a 3D network composed of a 1D chains composed of Bi2O8 dimers that are further bridged by Ge2O7 dimers, forming tunnels of seven member rings (MRs) that are filled by the Cs+ cations. CBGO exhibits extraordinary larger second harmonic generation (SHG) response of about 13.7 times that of KDP (KH2PO4) under 1064 nm laser radiation and 1.1 times that of KTP (KTiOPO4) under 2.05 mu m laser radiation, which is the highest among all of the metal germanates reported so far. CBGO possesses a moderate birefringence (0.073 at 1064 nm) and is phase matchable. Furthermore, CBGO melts congruently and exhibits high thermal stability.

The first examples of rare-earth polyiodates, namely, REI5 O14 (RE=Y and Gd), have been prepared by hydrothermal reactions of RE2 O3 and H5 IO6 in H3 PO4 (≥85 wt % in H2 O), with extremely high yields (>95 %). They crystalize in the polar space group Cm and feature a brand-new semicircle-shaped [I5 O14 ]3- pentameric polyiodate anion composed of two IO3 and three IO4 polyhedra. Remarkably, both compounds exhibit very large second-harmonic generation (SHG) signals (14× and 15×KH2 PO4 (KDP) upon 1064 nm laser radiation for Y and Gd compounds, respectively). Our work shows that the hydrothermal reaction in a phosphoric acid medium facilitates the formation of rare-earth polyiodates.

The first examples of bismuth fluoride selenites with d0 -TM/TeVI polyhedrons, namely, Bi4 TiO2 F4 (SeO3 )4 (1), Bi4 NbO3 F3 (SeO3 )4 (2), Bi4 TeO4 F2 (TeO3 )2 (SeO3 )2 (3), Bi2 F2 (MoO4 )(SeO3 ) (4) and Bi2 ZrO2 F2 (SeO3 )2 (5) have been successfully synthesized under hydrothermal reactions by aliovalent substitution. The five new compounds feature three different types of structures. Compounds 1-3, containing TiIV , NbV and TeVI respectively, are isostructural, exhibiting a new 3D framework composed of a 3D bismuth oxyfluoride architecture, with intersecting tunnels occupied by d0 -TM/TeVI octahedrons and selenite/tellurite groups. Interestingly, compound Bi4 TeO4 F2 (TeO3 )2 (SeO3 )2 (3) is the first structure containing SeIV and mixed-valent TeIV /TeVI cations simultaneously. Compound 4 features a new 3D structure formed by a 3D bismuth oxyfluoride network with MoO4 tetrahedrons and selenites groups imbedded in the 1D tunnels. Compound 5 displays a novel pillar-layered 3D open framework, consisting of 2D bismuth oxide layers bridged by the [ZrO2 F2 (SeO3 )2 ]6- polyanions. Theoretical calculations revealed that the five compounds displayed very strong birefringence. The birefringence values of compounds 1-3, especially, are above 0.19 at 1064 nm, which are larger than the mineral calcite. Based on the structure and property analysis, it was found that the asymmetric SeO3 groups (and TeO3 in compound 3) displayed the largest anisotropy, compared with the bismuth cations and the d0 -TM/Te polyhedra, which is beneficial to the birefringence.

To develop new mid-infrared (MIR) nonlinear optical (NLO) materials, which can overcome the low laser damage threshold (LDT) of the commercial MIR-NLO crystals (AgGaS2 , AgGaSe2 and ZnGeP2 ) and simultaneously keep the large NLO susceptibility, is necessary for high-power MIR laser frequency conversion technology. To improve the LDT, a new strategy of increasing lattice stability was adopted. Here, the strongly covalent structural unit of the PS4 tetrahedron was introduced into AgGaS2 (AGS), and that led to the isolation of the first compound in AgI -GaIII -PV -S system, namely, AgGa2 PS6 (Cc). It retains a large SHG efficiency (1.0×AGS) with phase-matchable ability, and also exhibits an improved LDT (5.1×AGS), indicating AgGa2 PS6 is a new promising MIR-NLO crystal. Moreover, a novel 3D framework of [Ga2 PS6 ]- , with triangular-shaped channels, as well as interesting single triangular geometry of AgS3 -both of which are very rare in reported sulfides-was discovered in AgGa2 PS6 . Furthermore, theoretical calculations, and lattice energy and thermal expansions analyses suggest that the PS4 group makes a large contribution to the large SHG efficiency and high LDT.

The first metal iodate fluoride, Bi(IO3)F2, with a strong second harmonic generation (SHG) effect has been prepared. Bi(IO3)F2 crystallizes in the polar space group C2 and features a three-dimensional [BiF2]+ cationic framework with IO3 groups capping the inner walls of the one-dimensional tunnels. This [BiF2]+ cationic framework acts as a template for the assembly of the polar IO3 units in a favorable superposed fashion, which leads to the polar structure of the material. Bi(IO3)F2 displays a rather wide transmittance window (0.3–11 μm) and exhibits a very strong SHG response that is about 11.5 times larger than that of KH2PO4 (KDP) under 1064 nm laser radiation and the same as that of KTiOPO4 (KTP) under 2.05 μm laser radiation. Preliminary investigations indicate that Bi(IO3)F2 is a promising nonlinear optical material in the visible and mid-IR region.

Semiconducting ferroelectricity is realized in hybrid perovskite-type compounds (cyclohexylammonium)2 PbBr4-4 x I4 x (x = 0-1). By adjusting the composition x, the bandgap is successfully tuned from previously reported 3.65 eV to as low as 2.74 eV, and the excellent ferroelectricity was kept intact. This finding may contribute to improving the photoelectronic and/or photovoltaic performance of hybrid perovskite-type compounds.

A series of lanthanide boroantimonates, namely, LnBSb2O8 (Ln = Sm 1, Eu 2, Gd 3, and Tb 4) have been successfully synthesized by high temperature solid-state reactions for the first time. They are isostructural and feature novel three-dimensional (3D) frameworks composed of 2D [Sb3O12]9– layers interconnected by 1D [SbBO7]6– chains with remaining BO3 groups hanging on the walls of the 1D 6-membered-ring (MR) tunnels along the a-axis, and the lanthanide ions filled in the voids of the anionic structure. They exhibit high thermal stability (up to 900 °C). Luminescent studies suggest that compounds 1, 2, and 4 have potential application as orange, red, and green light luminescent materials, respectively. Magnetic measurements reveal ferromagnetic coupling interactions in compound 3 and antiferromagnetic coupling interactions between magnetic centers in compounds 1, 2, and 4.

Single crystals of the title compound are prepared by hydrothermal reaction of a 1:5 molar mixture of Bi2O3 and SeO2 in 40% aq.

Systematic explorations of new phases in the Ag+–Ti4+/Zr4+/Nb5+/Ta5+–Se4+–O(F) system by hydrothermal syntheses or standard high temperature solid-state reactions resulted in four new mixed-metal silver selenites, namely, Ag3Ti3O3(SeO3)4F (1, P63), Ag2ZrF2(SeO3)2 (2, Cmca) and AgMO(SeO3)2 (M = Nb, 3; Ta, 4) in the space group Cmcm. Ag3Ti3O3(SeO3)4F features an interesting [Ti3O3(SeO3)4]2− 3D anionic framework composed of 1D chains of corner-sharing TiO6 octahedra which are further interconnected by tridentate bridging SeO32− anions, displaying 1D hexagonal channels of Ti6Se6 12-member rings (MRs) along the c-axis, filled by the Ag+ cations and isolated F− anions. More interestingly, it displays a moderate strong Second-Harmonic Generation (SHG) response about 2 times that of KH2PO4 (KDP). Compound 2 features a novel 1D [ZrF2(SeO3)2]2− anionic chain composed of edge-sharing ZrO4F4 polyhedra in which two neighboring Zr4+ cations are further bridged by a pair of selenite anions. Compounds 3 and 4 are isostructural and their structures feature 1D anionic chains of [MO(SeO3)2]− (M = Nb, Ta) which are separated by Ag+ cations, the 1D [MO(SeO3)2]− (M = Nb, Ta) chain is formed by 1D chains of corner-sharing MO6 (M = Nb, Ta) octahedra in which two neighboring metal centers are also bridged by a pair of selenite anions. Other characterizations including thermal analyses, optical and luminescence property measurements have also been performed.

The first examples of mixed-anion lanthanide galloborates, namely, Ln2Ga[B3O6(OH)]2[B7O9(OH)2](CH3CO2)2 [Ln = Y (1), Sm (2), Eu (3), Gd (4), Dy (5)], have been obtained through hydrothermal synthesis. The title compounds are isomorphic and belong to monoclinic space group C2/c (No. 15). Their structures possess [B7O13(OH)2] borate layers further bridged with [B3O7] clusters to give a three-dimensional (3D) borate framework displaying two types of rhombus-like B14O14 14-membered-ring (14-MR) channels along the b axis. The Ga3+ ions are octahedrally coordinated and located at one end of the B14O14 14-MR channels, forming small tunnels of B7Ga 8-MRs, which are filled by the LnIII ions. The Ln ions and Ga cations are further held together by bridging acetate anions. It is worth noting that in these compounds there are two different types of borate clusters and two types of anions that are uncommon in the borates reported. Luminescent studies revealed the characteristic emission bands of Ln ions for compounds ...

CsV2(H3O)(HPO3)4 (I) and Ba3V2(HPO3)6 (II) are prepared by hydrothermal reaction of aqueous Cs2CO3 or BaCO3, NaVO3, and H3PO3 (autoclave, 210 °C, 4 d, pH 0.5→1; 83 and 85% yield, resp.).

A new series of platinum iodates, namely, α-(H3O)2Pt(IO3)6, β-(H3O)2Pt(IO3)6, and A2Pt(IO3)6 (A = Na, K, Rb, Cs), have been synthesized. Interestingly, among these six stoichiometrically identical compounds, α-(H3O)2Pt(IO3)6 is polar, whereas other compounds are nonpolar and centrosymmetric. They all consist of zero-dimensional [Pt(IO3)6]2– molecular units separated by H3O+ or A+ cations. All of the lone electron pairs of the IO3– groups are aligned and almost point to one direction for α-(H3O)2Pt(IO3)6, whereas IO3– groups are located trans to each other in other compounds. The material, α-(H3O)2Pt(IO3)6, exhibits very strong second harmonic generation (SHG) effects, approximately 1.2 × KTiOPO4 (KTP), and is phase-matchable. Thermogravimetric analysis, elemental analysis, infrared spectra, UV–vis spectra, nonlinear optical properties, and theoretical calculations are also reported.

The first example of SHG crystal in the metal bromates containing π-conjugated planar triangle systems, namely, Pb4(OH)4(BrO3)3(NO3), was successfully synthesized via the hydrothermal method. Furthermore, a single crystal of centrosymmetric Pb8O(OH)6(BrO3)6(NO3)2·H2O was also obtained. Both compounds contain similar [Pb4(OH)4] cubane-like tetranuclear clusters, but they display different one-dimensional (1D) chain structures. Pb4(OH)4(BrO3)3(NO3) features a zigzag [Pb4(OH)4(BrO3)3](+) 1D chain, while Pb8O(OH)6(BrO3)6(NO3)2·H2O is composed of two different orthogonal chains: the linear [Pb4(OH)4(BrO3)2](2+) 1D chain along the b-axis and the zigzag [Pb4O2(OH)2(BrO3)4](2-) 1D chain along the a-axis. The NO3 planar triangles of the compounds are all isolated and located in the spaces of the structures. Pb4(OH)4(BrO3)3(NO3) exhibits the first example of SHG crystal in the metal bromates with π-conjugated planar triangle. The second-harmonic generation (SHG) efficiency of Pb4(OH)4(BrO3)3(NO3) is approximately equal to that of KDP and it is phase-matchable. Dipole moment and theory calculations indicate that BrO3, NO3, and PbO4 groups are the origin of its SHG efficiency, although some of the contributions cancel each other out.

Solid-state reactions of zinc(II) or cadmium(II) oxide, V(2)O(5), and TeO(2) at high temperature led to two novel quaternary compounds, namely, Zn(3)V(2)TeO(10) and Cd(4)V(2)Te(3)O(15). The structure of Zn(3)V(2)TeO(10) is a complicated three-dimensional (3D) network constructed by the interconnection of ZnO(5), ZnO(6), VO(4), and TeO(4) polyhedra via corner- and edge-sharing. Cd(4)V(2)Te(3)O(15) with an acentric structure features a 3D network in which the cadmium tellurite layers are further interconnected by both "isolated" VO(4) tetrahedra and one-dimensional (1D) vanadium oxide helical chains. Cd(4)V(2)Te(3)O(15) displays a second harmonic generation (SHG) efficiency of about 1.4 times that of KH(2)PO(4) (KDP). Both compounds are direct band-gap semiconductors and are transparent in the range of 0.6-10.0 mum. Measurements of luminescence indicate that both compounds exhibit broad emission bands in the blue-light region.

KCdCO3F (I) is prepared by solvothermal reaction of Cd(OAc)2, KF, and TFA in MeOH (Cd:K = 1:16; autoclave, 180 °C, 48 h; cooling to 20 °C at a rate of 2 °C/h, 63% yield).

The new compounds (IV) and (V) are prepared by solid state reactions and characterized by single crystal XRD, IR and UV/VIS spectroscopy, second harmonic generation measurements, and DFT electronic structure calculations.

Hydrothermal reactions of lanthanide nitrates with selenic acid, sodium oxalate, and organic amines led to two series of new organically templated lanthanide oxalate-selenate hybrids with 2D-layer or 3D-network structures, namely, Ln(2)(SeO4)(2)(C2O4)(H2O)(4)center dot pip (Ln = Eu 1; Tb 2; Dy 3; Er 4; Yb 5) (pip = piperazine) and [H(2)PiP](2)[Ln(2)(SeO4)(2)(C2O4)(3)]center dot H2O (Ln = Er 6; Yb 7; Lu 8; Y 9). Their structures were established by X-ray single-crystal diffraction. Isostructural compounds 1-5 feature a 2D inorganic-organic hybrid neutral layer of Ln(2)(SeO4)(2)(C2O4)(H2O)(4). The neutral piperazine molecules are located at the interlayer spaces and interconnect with the inorganic skeleton through hydrogen bonds. Compounds 6-9 are isostructural and possess 3D pillared layered architectures composed of lanthanide oxalate layers bridged by selenate anions (the pillar). The template cations are located at the tunnels of the structure. Compounds 1, 2, and 3 display emission bands in the red-, green-, and pink-light regions, respectively, and these compounds have lifetimes of 0.178, 0.962, and 0.276 ms, respectively. Compounds 6 and 7 both exhibit emission bands in the near-IR region. ((c) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)

Five new lead(II) sulfonate-phosphonates, namely [Pb(3)(L)(2)(H(2)O)(2)]center dot 4H(2)O (1), [Pb(HL)(phen)]center dot H(2)O (2), [Pb(6)(L)(4)(phen)(8)]center dot 3H(2)O (3), [Pb(6)(L)(4)(phen)(10)]center dot 2H(2)O (4), and [Pb(6)(L)(4)(4,4'-bipy)(H(2)O)(2)]center dot 2H(2)O (5; H(3)L = m-HO(3)S-C(6)H(4)-PO(3)H(2), phen = 1,10-phenanthroline, 4,4'-bipy = 4,4'-bipyridine) have been prepared and structurally characterized. Compound I features a novel 3D framework in which 1D chains of Pb(3)O(4) cluster units are further bridged by sulfonate-phosphonate ligands, whereas compound 2 features a layer structure in which 1D chains of Pb(2)O(4) clusters are further bridged by sulfonate-phosphonate ligands. Compounds 3 and 4 represent the first zero-dimensional lead(II) phosphonates and feature novel isolated hexanuclear lead(II) clusters in which six Pb(II) ions are bridged by two tetradentate and two pentadentate phosphonate groups. Compound 5 features a 3D framework that is similar to that in compound 1 despite the different coordination modes for some sulfonate groups of the ligands. The main difference is that an aqua ligand in compound 1 is replaced by a nitrogen atom of the 4,4'-bipy ligand, which results in the splitting of the large cavities in compound I into two small apertures in compound 5. Compounds 1 and 5 exhibit strong broad blue fluorescent emission bands at 398 and 420 nm, respectively. ((c) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheirn, Germany, 2007).

Large crystals of Cs2TeW3O12 (20 x 15 x 4 mm) are grown by the top-seeded solution growth method from mixtures of Cs2TeW3O12 and Cs2O and TeO2 as a flux (molar ratio1:1:4) or Cs2CO3, TeO2, and WO3 (molar ratio of 2:5:3) (Pt crucible, 700 °C, 3 d).

The new compound (III) crystallizes in the orthorhombic space group Cmc21 with Z = 8 (powder XRD).

Single crystals of Pb2(BO3)(NO3) are prepared by hydrothermal reaction of Pb(NO3)2 and Mg(BO2)2 at pH 5.0-5.5 (autoclave, 210 °C, 4 d; 85% yield).

The title compounds are prepared by solid state reactions of Na2CO3, TeO2, H3BO3, and Ln2O3 (Ln: Y, Dy—Lu; Pt crucible, 830 °C, 10 d).

Hydrothermal reactions of different lanthanide(III) salts with (H 2 O 3 PCH 2 ) 2 NCH 2 COOH (H 5 L 1 ) led to two new layered lanthanide(III) carboxylate-diphosphonates, namely La-(H 2 L 1 )(H 2 O) 2 ·H 2 O (1) and La(H 2 L 1 )(H 2 O) (2). The structure of compound 1 features a layered architecture in which the nine-coordinate La 3+ ions are bridged by phosphonate groups of the ligands. The carboxylate group of the phosphonate ligand remains protonated and is involved in the interlayer hydrogen bonding. Compound 2 features a double layer structure in which the La 3+ ion is eight-coordinated and the carboxylate group of the ligand is chelated to a La 3+ ion in a bidentate fashion. Hydrothermal reactions of lanthanide(III) salts with 4-HOOC-C 6 H 4 -CH 2 N(CH 2 PO 3 H 2 ) 2 (H 5 L 2 ) afforded three new compounds, namely, La(H 4 L 2 )(H 3 L 2 )-(H 2 O)·2H 2 O (3), Er(H 3 L 2 )(H 4 L 2 ) (4), and Er(HL 3 )(H 2 L 3 )(H 2 O) (5) [H 2 L 3 = H 2 O 3 PCH 2 N(CHO)(CH2-C6H4-COOH)]. H 2 L 3 was formed by the in situ oxidation of one P-C bond of the H 5 L 2 ligand. Compound 3 features a (002) lanthanum(m) phosphonate layer in which the seven-coordinate La 3+ ions are bridged by diphosphonate moieties of the ligands. The carboxylate group remains protonated and is involved in the interlayer hydrogen bonding. The structure of compound 4 contains a 1D chain along the a axis in which each pair of ErO 6 octahedra is bridged by a pair of phosphonate groups. These 1D chains are further interconnected by hydrogen bonds between noncoordinated phosphonate oxygen atoms into a (002) layer with the phenyl carboxylate groups hanging on the interlayer space. The structure of compound 5 is also layered. The interconnection of Er 3+ ions by bidentate and tetradentate bridging phosphonate groups resulted in a (002) inorganic layer with the organic groups orientated to the interlayer space. Luminescence properties of compounds 4 and 5 have also been studied.

Hydrothermal reactions of the lanthanide chlorides with MeN(CH2CO2H)(CH2PO3H2), (H3L1) (or Me2NCH2PO3H2, H2L2) and sodium oxalate lead to seven new lanthanide oxalate phosphonate hybrids with three types of 3D network structures, namely, [Ln(C2O4){MeNH(CH2CO2)(CH2PO3H)}]0.5 H2O (Ln=Nd: 1; Eu: 2; Gd: 3), [Ln4(C2O4)5(Me2NHCH2PO3)2(H2O)4]2 H2O (Ln=La: 4, Nd: 5), [Ln3(C2O4)4(Me2NHCH2PO3)(H2O)6]6 H2O (Gd: 6, Er: 7). Their structures have been established by X-ray single-crystal diffraction. Complexes 1-3 are isostructural and feature a 3D network formed by the interconnection of 3D network of {Ln(H2L1)}2+ with 1D chains of {Ln(C2O4)}+. Complexes 4 and 5 are isostructural and feature a complex 3D network built from 3D network of lanthanide oxalate and {Ln4(HL2)2} units. The isostructural 6 and 7 form another type of 3D network composed of porous lanthanide-oxalate network inserted by 1D chains of lanthanide-oxalate phosphonate. Compounds 1, 5 and 7 are luminescent materials in the near IR region. Compounds 3 and 6 exhibit a broad blue fluorescent emission band at 451 and 467 nm, respectively. Compound 2 displays very strong and sharp emission bands at 592, 616 and 699 nm with a long luminescent lifetime of 1.13 ms.

The hydrothermal syntheses and crystal structures of two novel cobalt carboxylate−phosphonates with 4,4′-bipyridine (4,4′-bipy) as the secondary metal linker are reported. Compound 1, [Co3(H2L)2(H2O)4(4,4′-bipy)], where H5L = 4-HO2CC6H4CH2N(CH2PO3H2)2, crystallizes in the monoclinic space group C2/c with a = 25.9281(5), b = 9.76310(10), c = 17.3671(5) A, β = 103.290(2)°, V = 4278.6(2) A3, and Z = 4. Its structure contains a pillar-layered architecture in which CoII octahedra are linked by carboxylate−phosphonate ligands to form a 2D layer and these layers are crosslinked further by 4,4′-bipy ligands to form a porous 3D network. Compound 2, [Co2(PMIDA)(H2O)5(4,4′-bipy)]·4H2O, where H4PMIDA = H2O3PCH2N(CH2CO2H)2, crystallizes in the triclinic space group P with a = 7.8009(7), b = 13.4560(12), c = 13.5453(12) A, α = 65.207(2), β = 88.035(2), γ = 77.135(2)°, V = 1255.57(19) A3, and Z = 2. The crystal structure of compound 2 contains 1D zigzag chains in which two cobalt(II) ions are bridged by PMIDA ligand to form dimeric units, and these dimeric units are connected further by bridging 4,4′-bipy ligands. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)

The hydrothermal reaction of lead(II) carbonate with 3-sulfobenzoic acid, 3-HO3S−C6H4−CO2H, and isopropylimino-bis(methylenephosphonic acid), (CH3)2CHN(CH2PO3H2)2 (H4L1), gave a new layered lead(II) carboxylate-phosphonate, Pb7(3-O3S−C6H4−CO2)(L1)3(H2O)2·2H2O (1), whereas the hydrothermal reaction of lead(II) carbonate with 1, 3,5-benzenetricarboxylic acid (H3BTC) and N-cyclohexylimino-bis(methylenephosphonic acid), C6H11N(CH2PO3H2)2 (H4L2), afforded a layered complex, Pb3(HL2)(H2L2)(H2BTC)(H2O)·H3BTC·H2O (2). The structure of complex 1 contains lead(II) carboxylate-phosphonate hybrid layers, with the sulfonate group of the carboxylate-sulfonate ligand as the pendant group. In complex 2, the lead(II) ions are interconnected through bridging diphosphonate ligands, and results in the formation of a lead(II) diphosphonate slab, which are further interlinked via hydrogen bonds between non-coordinated phosphonate oxygen atoms to form a layer. The doubly protonated H2BTC anion is bidentately chelated to a lead(II) ion through a carboxylate group, whereas the neutral H3BTC ligand is intercalated between two layers, forming hydrogen bonds with the non-coordinated carboxylate groups of the H2BTC anion. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)

Four heteronuclear CuII−HgII halides containing 2,2-bipyridine (bipy) ligands have been synthesized and structurally characterised by single-crystal X-ray diffraction studies. The dinuclear complex [Cu(bipy)2HgCl2Br2] (1) contains a five-coordinate copper(II) ion and a four-coordinate HgII ion, in which the two different types of metal ions are bridged by a pair of chloride anions. [Cu2(bipy)4HgBr4][Hg2Br6] (2) contains a trinuclear [Cu2(bipy)4HgBr4]2+ cation in which the two copper(II) ions are bridged by an [HgBr4]2− tetrahedron via two Cu−Br bonds, and an edge-sharing tetrahedral [Hg2Br6]2− anion. The structure of [Cu2(bipy)4Hg2Br6][Hg4Br10] (3) features a 1-D chain along the diagonal of the a and c axes constructed from tetranuclear [Cu2(bipy)4Hg2Br6]2+ cations interconnected by [Hg4Br10]2− tetramers via elongated Hg−Br contacts (3.185 A). Within the tetranuclear cationic unit, two [Cu(bipy)2]2+ units are bridged by an edge-sharing dimeric tetrahedral [Hg2Br6]2− anion. In the trinuclear complex [Cu(bipy)2Hg2Cl6] (4), each [Hg2Cl6]2− dimer bridges with a [Cu(bipy)2]2+ ion to form a trinuclear [Cu(bipy)2Hg2Cl6] unit, and each pair of such units is bridged by a pair of elongated Hg−Cl bonds [3.043(5) A] to form a dimeric unit. The magnetic properties of 1, 2, and 4 have also been investigated. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)

Hydrothermal reactions of lead(II) acetate with 1,3,5-benzenetricarboxylic acid (H3BTC) and a new aminodiphosphonic acid, [3-pyridyl-CH2N(CH2PO3H2)2] (H4L1), or a new aminotriphosphonic acid, [1-{(H2O3PCH2)2NCH2CH2-}-piperazine-4-CH2PO3H2] (H6L2), afforded two novel porous carboxylate−phosphonate hybrids, [Pb4(BTC)(HBTC)(HL1)]·3H2O (1) and [Pb6(BTC)2(HBTC)(H2L2)]·4.5H2O (2). The structure of 1 is built from a 3D porous network of lead(II) tricarboxylate and 1D double chains of lead(II) aminodiphosphonate. The structure of 2 contains lead(II) carboxylate−phosphonate hybrid layers, which are cross-linked by 1D double chains of lead(II) phosphonate through the organic groups of both types of ligands, resulting in the formation of a complex 3D porous network. The lattice water molecules in both compounds are located at the micropores of the structures. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)

The new title compounds (III) and (V) are characterized by single crystal XRD, IR, UV/VIS, and optical diffuse reflectance spectroscopy, second harmonic generation measurements, and DFT electronic band structure calculations.

The new compounds (IV), (VI), (VII), and (VIII) are characterized by single crystal XRD, IR and UV spectroscopy, and DFT band structure calculations.

The layered iodate Cd(IO3)Cl (I) is prepared by hydrothermal reaction of CdCl2 and I2O5 (H2O, autoclave, 200 °C, 4 d, 82% yield).

The new compounds (III), (VI), and (VII) are characterized by single crystal XRD, UV/VIS and IR spectroscopy, second harmonic generation measurements, and DFT electronic structure calculations.

The noncentrosymmetric isomeric polyiodates α-AgI3O8 (I) and β-AgI3O8 (II) are prepared by hydrothermal reactions of AgNO3 with I2O5 in molar ratios of 1:160 and 1:16, respectively.

Single crystals of the title compounds are prepared by solid state reaction of K2CO3 or Ba(OH)2, Sb2O3, and H3BO3 (Pt crucibles, 850 °C, 33 h).

Two new rubidium iodates, namely, β-RbIO3(HIO3)2 (1, P1) and Rb3(IO3)3(I2O5)(HIO3)4(H2O) (2, P21/c), have been synthesized by hydrothermal reaction and their structures determined by single-crystal X-ray diffraction. Compound 1 exhibits IO3– anions and neutral HIO3 molecules which are interconnected by Rb+ cations into three-dimensional structure. Compound 2 features a two-dimensional layered structure formed by IO3– anions and neutral HIO3 and dimeric I2O5 molecules interconnected by Rb+ cations. Large bulk crystal of 1 with dimensions of several millimeters has been grown. UV–vis–NIR transmission spectroscopy measurements on a slab of a polished crystal of 1 indicated that the crystal possesses a short-wavelength absorption edge onset at 305 nm. Powder second-harmonic generation (SHG) measurements on sieved crystals revealed that 1 is a type I phase-matchable material with an SHG response about 1.5 times that of KH2PO4. The Vickers hardness of crystal of 1 has been measured to be 110 HV, and the laser-i...

SrGe2B2O8 (I) and Sr3Ge2B6O16 (II) are synthesized by solid state reaction of stoichiometric mixtures of SrCO3, GeO2, and H3BO3 (Pt crucible, 900 °C, 3 d).