Guo-Yu Yang

Structural Transformation from Dimerization to Tetramerization of Serine-Decorated Rare-Earth-Incorporated Arsenotungstates Induced by the Usage of Rare-Earth Salts

Three types of serine-decorated rare- earth-containing arsenotungstate [H2 N(CH3 )2 ]6 NaH[RE2 W4 O10 (H2 O)8 (Ser)2 (B-α-AsW9 O33 )2 ]⋅30u2009H2 O (RE3+ =Eu3+ , Gd3+ , Tb3+ , Dy3+ , Ho3+ , Er3+ , Tm3+ , Yb3+ , and Y3+ ; 1), [H2 N(CH3 )2 ]6 Na6-x REx H4-2u2009x [RE4 W8 O19 (H2 O)10+y (OH)2 (Ser)2 (B-α-AsW9 O33 )4 ]⋅nu2009H2 O (RE3+ =Tb3+ , x=1, y=2, n=36; RE3+ =Dy3+ , Ho3+ , Er3+ , Yb3+ , Y3+ , x=0, y=0, n=38; RE3+ = Tm3+ , x=1, y=0, n=38; Ser=serine; 2), and [H2 N(CH3 )2 ]6-2u2009x Na2+3u2009x REx H10-6u2009x+y [RE4 W8 O19 (H2 O)8 (OH)2 (Ser)4 (B-α-AsW9 O33 )4 ]⋅Cly ⋅nu2009H2 O (RE3+ =Ce3+ , Pr3+ , x=1, y=0, n=65; RE3+ =Nd3+ , Sm3+ , x=0, y=0, n=65; RE3+ =Eu3+ , Gd3+ , x=1, y=2, n=45; 3) were synthesized with the participation of the organic solubilizers dimethylamine hydrochloride and l-serine and were structurally characterized. The use of different amounts of rare-earth salts results in the structural transformation from dimerization to tetramerization of types 1-3. Type 1 is a dimeric sandwich-type assembly of a dual-Ser-participating [RE2 W4 O10 (H2 O)8 (Ser)2 ]10+ entity sandwiched by two [B-α-AsW9 O33 ]9- moieties, whereas types 2 and 3 have a tetrameric square structure formed by four [B-α-AsW9 O33 ]9- moieties that anchor a dual/tetra- Ser-participating [RE4 W8 O19 (H2 O)10+y (OH)2 (Ser)2 ]20+ or [RE4 W8 O19 (H2 O)8 (OH)2 (Ser)4 ]20+ core. The solid-state luminescence properties and lifetime-decay behaviors of these compounds were investigated. The chromaticity coordinates, dominant wavelengths, color purities, and correlated color temperatures were also calculated.

Supramolecular nanotubes constructed from 3d–4f heterometallic sandwiched polyoxotungstate dimers

By the hydrothermal technique, a series of organic–inorganic hybrid polyoxometalates (POMs) Hx(H2en)y [Fe2Ln(β-PW10O37)2(Tart)]·nH2O (Ln = La3+, (x, y, n) = (5, 3, 9) for 1; Ln = Ce3+, (x, y, n) = (5, 3, 7) for 2; Ln = Sm3+, (x, y, n) = (3, 4, 25) for 3; Ln = Tb3+, (x, y, n) = (3, 4, 21) for 4; H2Tart = tartaric acid) have been obtained and structurally characterized by elemental analyses, IR spectroscopy, thermogravimetric analyses and single-crystal X-ray diffraction. The common structural characteristics of 1–4 consist of a [Fe2Ln(β-PW10O37)2(Tart)]9− unit, in which transition metal and lanthanide ions co-exist in the vacant site of divacant [β-PW10O37]9− with the assistance of Tart ligands. It should be pointed out that 1–4 represent the first 3d–4f heterometallic cluster sandwiched phosphotungstate dimers, [Fe2Ln(β-PW10O37)2(Tart)]9−, linked by Fe–O–Ln–O–Fe bonds. Furthermore, 3 and 4 exist as rare supramolecular nanotubes built from the organic–inorganic hybrid 3d–4f POM units. Also, the photochromism and optical properties of 1–4 have been studied.

Linking 1D Transition-Metal Coordination Polymers and Different Inorganic Boron Oxides To Construct a Series of 3D Inorganic–Organic Hybrid Borates

Three inorganic-organic hybrid borates, M(1,4-dab)[B5O7(OH)3] [M = Zn (1), Cd (2), 1,4-dab = 1,4-diaminobutane)] and Co(1,3-dap)[B4O7] (3, 1,3-dap = 1,3-diaminopropane), which integrated characteristics of 1D coordination polymers and 1D/3D inorganic boron oxides have been obtained under solvothermal conditions. Compounds 1 and 2 are isostructural and crystallize in a centrosymmetric space group P21/c; the 3D achiral structures of 1 and 2 consist of the nonhelical Zn/Cd-1,4-dap coordination polymers and 1D B-O chains. Compound 3 crystallizes in a chiral space group P43212; the helical Co-1,3-dap coordination polymer chains are entrained within a 3D B-O network and finally form the chiral framework. Compounds 1-3 represent good examples of using coordination polymers to construct mixed-motif inorganic-organic hybrid borates. Compounds 1 and 2 display blue luminescence when excited with UV light.

Two New Octaborates Constructed of Two Different Sub-clusters and Supported by Metal Complexes

Two inorganic–organic hybrid borates, [Zn(en)2{B8O11(OH)4}] (1, enxa0=xa0ethylenediamine) and [Cd(TREN){B8O11(OH)4}] (2, TRENxa0=xa0tris(2-aminoethyl)amine) have been made under hydro(solvo)thermal conditions and characterized by IR spectroscopy, elemental analysis, single crystal X-ray diffraction, diffuse-reflectance spectroscopy, thermogravimetric analyses, and powder X-ray diffraction. Crystal data for 1: triclinic, P−1, axa0=xa08.7091(5)xa0Å, bxa0=xa08.8731(2)xa0Å, cxa0=xa012.7642(8)xa0Å, αxa0=xa087.042(4)°, βxa0=xa078.198(5)°, γxa0=xa080.816(4)°, Vxa0=xa0952.96(9)xa0Å3. Crystal data for 2: monoclinic, P21/c, axa0=xa011.5051(4)xa0Å, bxa0=xa08.7879(4)xa0Å, cxa0=xa019.9322(7)xa0Å, βxa0=xa091.433(3)°, Vxa0=xa02014.63(14)xa0Å3. They both contain [B8O11(OH)4]2− cluster units, which linked each other to form 1-D chains. These 1-D chains are further joined together to produce 3-D supramolecular frameworks via H-bonding interactions. Interestingly, the [B8O11(OH)4]2− cluster in 1 is made of [B5O8(OH)2]3− and [B3O5(OH)2]2− sub-cluster units with two O atoms in common, while in 2 consists of [B5O7(OH)3]2− and [B3O6(OH)]4− sub-cluster units with two O atoms in common. The [B8O11(OH)4]2− ligands in 1 and 2 are coordinated to the supporting metal complexes in different ways. The anion in 1 is coordinated to the Zn(en)2 by a terminal OH group whereas the anion in 2 is coordinated by a bridging O atom. The in situ organic rearrangement reaction from triethylene tetramine (TETA) to tris(2-aminoethyl)amine (TREN) has been observed in the formation of 2.

[Zn(dap)3][Zn(dap)B5O8(OH)2]2: A Novel Organic–Inorganic Hybrid Chain-Like Zincoborate Made of [B5O8(OH)2]3− Clusters and [Zn(dap)]2+ Linkers

A new organic–inorganic hybrid chain-like zincoborate [Zn(dap)3][Zn(dap)B5O8(OH)2]2 (1, dapxa0=xa01,2-diaminopropane) has been made under solvothermal conditions. The structure was determined by single crystal X-ray diffraction and further characterized by elemental analysis, FT-IR, thermogravimetric analysis and photo-luminescence spectroscopy. Crystal data for 1: orthorhombic, Pca21 (No. 29), axa0=xa012.5696(4)xa0Å, bxa0=xa012.9506(6)xa0Å, cxa0=xa025.2370(10)xa0Å, Zxa0=xa04. The structure of 1 features one-dimensional (1-D) inorganic–organic hybrid zincoborate helical chain, which was constructed from the assembly of [B5O8(OH)2]3− clusters and Zn(dap) linkers. Adjacent zincoborate chains are further linked by [Zn(dap)3] complexes through extensive hydrogen-bonds to generate 3-D supramolecular network. Two distinct coordination-modes of zinc centers are simultaneously observed in the structure, and they play different roles in the formation of the resultant framework. In addition, 1 exhibits extensive luminescence and moderate second-harmonic generation efficiency.

Na4Ca[B4O5(OH)4]3·14H2O: An Acentric Supramolecular Framework Borate Based on [B4O5(OH)4]2− Cluster Units

A new mixed-metal tetraborate, Na4Ca[B4O5(OH)4]3·14H2O (1), with an acentric structure has been synthesized under mild solvothermal conditions and characterized by powder X-ray diffraction, thermogravimetric analysis, IR and UV–Vis spectroscopy, nonlinear optical determination and single crystal X-ray diffraction. 1 crystallizes in hexagonal space group P-62c (No. 190) with the unit cell parameters: axa0=xa011.2896 (6) Å, cxa0=xa015.8360 (9) Å, Vxa0=xa01748.0 (2) Å3, and Zxa0=xa01. The compound features two types of layered networks, a borate network with kgm topology and a Na–O–Ca network with hcb topology, which are alternately arranged generating a 3D framework with straight channels. Powder second-harmonic-generating measurement indicates that compound 1 presents a SHG response of ~0.9 times that of KDP (KH2PO4), with the UV cut-off edge below 240xa0nm, making 1 a potential UV NLO material.

[M(1,2-dap) 3 ][B 10 O 13 (OH) 6 ] (M = Co, Ni): Two New Borates Containing [B 10 O 13 (OH) 6 ] 2− Cluster Units

Two novel isomorphic decaborates, [M(1,2-dap)3][B10O13(OH)6] (Mxa0=xa0Co (1) and Ni (2); dapxa0=xa01,2-diaminopropane), with transition metal complexes [M(1,2-dap)3] as templates have been synthesized successfully under mild hydrothermal conditions and characterized by powder X-ray diffraction, thermogravimetric analysis, IR spectrum, single crystal X-ray diffraction and UV–Vis spectroscopy. The noodle-like orange/purple crystals crystallize in triclinic space group P-1. Their structure contain the isolated [B10O13(OH)6]2− clusters and further link together to produce a 3-D supramolecular framework with large channels by H-bonding interactions. The UV–Vis–NIR diffuse reflectance spectrum showed a wide-band-gap of 1 and 2. Notice that compounds 1 and 2 are not only the first isolated decaborate cluster and fill the gap left by the absence of isolated structures in the borate family but also could be considered as the structural building units to construct extended oxoboron cluster frameworks.

Two New Tetra-Zr(IV)-Substituted Sandwich-Type Polyoxometalates Functionalized by Different Organic Amine Ligands

By the hydrothermal technique, two new organic–inorganic hybrids, tetra-Zr-substituted sandwich-type germanotungstate clusters functionalized by different organic amines H10K4[Zr4(μ3-O)2(μ-OH)2(enMe)2(B-α-GeW10O37)2]·6DMF·18H2O (1) and H10K2Na2[Zr4(μ3-O)2(μ-OH)2(en)2(B-α-GeW10O37)2]·4 DMF·22H2O (2) (enMeu2009=u20091,2-diaminopropane, enu2009=u2009ethylenediamine, DMFu2009=u2009N,N-dimethylformamide) have been obtained, which have been characterized by single-crystal X-ray structure analysis, powder X-ray diffraction (PXRD), elemental analysis, FT-IR spectra and thermogravimetric analysis (TGA), respectively. The structure analysis reveals that 1 and 2 exhibit similar sandwich-type polyoxoanion built by two [Zr2(μ3-O)(μ-OH)(enMe)(B-α-GeW10O37)] or [Zr2(μ3-O)(μ-OH)(en)(B-α-GeW10O37)] clusters, showing the first germanotungstate clusters with Zr-containing 5-membered ring formed from the chelation coordination pattern of Zr4+ and organic amine. To compounds 1 and 2, the cluster units, [Zr4(μ3-O)2(μ-OH)2(enMe)2(B-α-GeW10O37)2] and [Zr4(μ3-O)2(μ-OH)2(en)2(B-α-GeW10O37)2], are linked by K+ cations to form 1-D chains, respectively.

Three Alumino/Galloborate Frameworks Templated by Organic Amines: Syntheses, Structures, and Nonlinear Optical Properties

A series of alumino/galloborates, including (H3APEA)6[Al-B5O10]9·12H2O (1, APEA = N, N-bis(3-aminopropyl)ethylenedi-amine), (HDETA)2(H2DETA)2[AlB5O10]3 (2, DETA = diethylenetriamine), and (H2EDAP)[GaB5O10]·H2O (3, EDAP = N-ethyl-diaminopropane), was solvothermally synthesized and characterized in solid-state by powder X-ray diffraction, Fourier transform infrared spectroscopy, UV-vis spectroscopy, and single-crystal X-ray diffraction. All of them feature the [MB5O10] n2 n- (M = Al or Ga) frameworks, charge-balanced by the long chain-like amine cations. Three frameworks exhibit different interlinkage modes of {MB5O10} layers, resulting in channels varying in size and shape. The flexibility of long chain-like amine cations as well as their significant structure-directing functions in forming these crystalline products is also discussed in detail. Powder second-harmonic generation measurements showed that all three compounds present a nonlinear optical property, and compound 2 exhibits type I phase-matchable optical nonlinearity.

Unprecedented Selenium and Lanthanide Simultaneously Bridging Selenotungstate Aggregates Stabilized by Four Tetra-vacant Dawson-like {Se2W14} Units

In the presence of the larger [H2 N(CH3 )2 ]+ and K+ counter cations as structure-stabilizing agents, a class of unprecedented selenium and lanthanide (Ln) simultaneously bridging tetra-vacant Dawson-like selenotungstate aggregates [H2 N(CH3 )2 ]2 Na9 K2 H19 {[Ln4 W4 Se4 O22 (H2 O)5 ](Se2 W14 O52 )2 }2 ⋅60u2009H2 O [Ln=TbIII (1), DyIII (2), HoIII (3), ErIII (4), TmIII (5), YbIII (6)] have been obtained by the one-pot assembly reaction of Na2 WO4 ⋅2u2009H2 O, Ln(NO3 )3 ⋅6u2009H2 O, and Na2 SeO3 under moderately acidic aqueous conditions and the complexes were structurally characterized by elemental analyses, IR spectra, single-crystal X-ray diffraction, powder X-ray diffraction (PXRD), and thermogravimetric (TG) analyses. It should be noted that the appropriate molar ratio of Se/W is extremely important in the formation of 1-6 and can effectively ameliorate the yield of 1-6. Moreover, dimethylamine hydrochloride is also indispensable and plays a considerably important role in improving the solubility of Ln ions and stabilizing the structures of 1-6. The main polyoxoanion skeletons of 1-6 are constructed from two sandwich-type tetra-vacant Dawson-like {[Ln4 W4 Se4 O22 (H2 O)5 ](Se2 W14 O52 )2 }16- half-units linked through two W-O-Ln bridges. The sandwich-type half-unit comprises two tetra-vacant Dawson-like [Se2 W14 O52 ]12- fragments encapsulating a unique dodecanuclear Se-Ln-W [Ln4 W4 Se4 O22 (H2 O)5 ]8+ oxo cluster. Their solid-state visible and NIR fluorescent properties and lifetime decay behaviors were measured and their solid-state luminescent spectra mainly demonstrate the characteristic emission bands of Ln3+ ions. Moreover, the dominant wavelengths, the color purity, and correlated color temperatures of 1-5 have been also calculated. In addition, the luminous flux values of 1-5 are 2031, 6992, 3071, 921, and 477u2005lumen, respectively.