•Three isomorphic 2D layered Ln-MOFs were constructed by flexible tricarboxylic acid.•A series of Eu3+/Tb3+ doped Ln-MOF 4 were fabricated and showed tunable luminescence.•Ln-MOF 2 exhibited excellent fluorescence sensing for small molecules.Three isomorphic lanthanide metal-organic frameworks (Ln-MOFs) [LnL(H2O)2]·2H2O (Ln=Tb for 1, Eu for 2, Gd for 3) have been constructed from flexible organic ligand 4-(2-carboxyphenoxy)benzene-1,3-dioic acid (H3L). They exhibit two-dimensional (2D) layered structure with the rhombus windows along the b axis. This network can be described as a shubnikov plane net with Schäfli symbol of (43)2(46.66.83). Solid state luminescent studies indicate that 1 and 2 show the characteristic red, and green emissions of the corresponding Ln3+ ions, respectively, while 3 exhibits blue emission arising from the organic ligand. Then by adjusting the relative amounts of different luminescent components into the well-defined host framework, a series of new co-doped Ln-MOF, Tb1−xEuxL (4) (x refers to the molar ratios of Eu3+ and Tb3+), with tunable luminescence have been fabricated. The luminescent color of 4 can be tuned from green to red due to the energy transfer from the Tb3+ to Eu3+ ions by changing the doping concentration of the Eu3+ ions. In addition, 2 exhibits good stability in different solvents and excellent fluorescence sensing for small molecules, especially for CH3CN and nitrobenzene.A series of isomorphic 2D layered Ln-MOFs have been constructed from flexible tricarboxylic ligand, showing tunable luminescence and excellent fluorescence sensing for small molecules, respectively.

•Two zinc(II) coordination polymers have been successfully synthesized.•1 and 2 perform as host to encapsulate Ln(III) ions and sensitize Tb(III) ions.•Both Eu0.2Tb0.8@1 and Eu3+@2 present white-light emission.•2 exhibits highly luminescent sensing properties for acetone.Two zinc(II) coordination polymers (CPs), namely, {[Zn2(µ5-tzbt)(µ-trz)]·3.5H2O}n (trz = 1,2,4-triazolate) (1) and {[Zn2(µ5-tzbt)(µ-OH)(phen)]·4H2O}n (phen = 1,10-phenanthroline) (2) have been constructed from 1-(triazol-1-yl)-2,4,6-benzene tricarboxylic acid (H3tzbt) under hydrothermal conditions. Single crystal X-ray diffraction analysis reveals that 1 displays 3D framework containing left - handed and right - handed helical chains, whilst 2 is a 2D layered structure. These new CPs both exhibit intensive fluorescence emission at room temperature. Notably, they perform as host for the encapsulation of Ln(III) ions and serve as an antenna to sensitize Tb(III) ions. By encapsulating different Ln(III) ions, both Eu0.2Tb0.8@1 and Eu3+@2 present white-light emission. In addition, 2 exhibits highly luminescent sensing properties for acetone.Two zinc(II) coordination polymers with 1-(triazol-1-yl)-2,4,6-benzenetricarboxylate ligand have been prepared under hydrothermal conditions. Notably, they perform as host for the encapsulation of Ln(III) ions and both Eu0.2Tb0.8@1 and Eu3+@2 present white-light emission. In addition, 2 exhibits highly luminescent sensing properties for acetone.Download high-res image (334KB)Download full-size image

A series of new lanthanide metal–organic frameworks (Ln-MOFs) [Ln2(L)3(H2O)4]·2H2O (1) (Ln = Eu, Tb, Gd), and [Gd2(H2O)4(L)(C2O4)2]·3H2O (2) were synthesized based on 4-hydroxypyridine-2,6-dicarboxylic acid (H2L) under hydrothermal conditions. 1 exhibits isomorphous 2D wave-like networks constructed by paddle-wheel [Ln(L)3] units and LnO4(H2O)4 polyhedra. 2 shows a (4,4)-connected 3D framework with a Schlafli symbol of 66. Oxalic acid in the resulting framework of 2 is formed in situ under hydrothermal conditions. Luminescence studies indicate that 1-Eu and 1-Tb show characteristic red and green emissions of the corresponding Ln3+ ions, respectively, while 1-Gd and 2 exhibit blue emission arising from the H2L ligand. Then, by adjusting the co-doping ratio of three different Ln3+ ions into the same framework as that of 1, a novel doped Ln-MOF, [(Eu0.0073Tb0.0007Gd0.992)2(H2O)4(L)3]·2H2O (3), is successfully designed and synthesized, which shows white light emission upon excitation at 340 nm and its emission can also be switched between different colors. In addition, 1-Gd shows weak ferromagnetic interactions.

•Two isostructural Ln-CPs were prepared by hexanuclear lanthanide complexes.•They feature a 3D framework containing novel octanuclear [Ln8(OH)8]16+ units.•They show the characteristic NIR emissions of Yb3+ and Er3+ ions in the solid-state.•Ln-CP 1 displays the antiferromagnetism in the range of 4–300 K.Two novel lanthanide coordination polymers (Ln-CPs), [Ln11(OH)8(4,4′-oba)12(CH3COO)2]·(CH3)2NH2·3DMF·nH2O, (Ln = Yb(1), Er(2), 4,4′-H2oba = 4,4′-oxybis(benzoic acid), DMF = N, N′-dimethylformamide, n = 2 for 1, 3 for 2) have been self-assembled from the reaction of hexanuclear lanthanide complexes with flexible V-shaped organic ligands under solvothermal condition. Structural analyses reveal that they are isomorphous and feature a complicated three-dimensional (3D) framework containing novel octanuclear [Ln8(OH)8]16+ units. Moreover, they show the characteristic luminescence emission bands of the corresponding lanthanide ions in the near-infrared regions in the solid-state. Additionally, magnetic property of 1 shows typical antiferromagnetic interactions.Two novel isomorphous Ln-CPs have been self-assembled from the reaction of hexanuclear lanthanide complexes with flexible V-shaped organic ligand under solvothermal condition. They feature a complicated 3D framework containing novel octanuclear [Ln8(OH)8]16+ units and show the characteristic NIR emissions of the corresponding lanthanide ions in the solid-state.

•A series of lanthanide coordination polymers have been successfully under hydrothermal/solvothermal conditions.•The H3POIDC ligand deriving from H3PIDC ligand in situ reaction, as firstly reported in Ln-CPs.•Compounds 1–6 show strong luminescence emission in solid state, especially compound 1 exhibits obvious luminescence quenching for Hg2+ ion.A series of novel lanthanide coordination polymers (Ln-CPs) have been constructed by 2-(pyridin-2-yl-N-oxide)-1H-imidazole-4,5-dicarboxylate (H3POIDC) ligand, which derived from the partial oxidation of 2-(pyridin-2-yl)-1H-imidazole-4,5-dicarboxylate (H3PIDC) in situ reaction. Compounds 1–3 with the infinite left- and right-hand helices show 3D supramolecular structure constructing from 1D chains connecting each other through strong hydrogen-bond interactions. Compounds 4–7 show 2D layered structure with sql topology which are built from 4-connected nodes. Moreover, compounds 1–6 show strong luminescence emission in solid state, especially compound 1 exhibits obvious luminescence quenching for Hg2+ ion.Based on in situ reaction of 2-(pyridin-2-yl)-1H-imidazole-4,5-dicarboxylate, a series of novel lanthanide coordination polymers have been successfully synthesized under hydrothermal/solvothermal conditions and exhibit two different structures. Moreover, compounds 1–6 show strong luminescence emission in solid state, especially compound 1 exhibits obvious luminescence quenching for Hg2+ ion.

•Two new isostructural lanthanide coordination polymers (Ln-CPs) with two kinds of one-dimensional channels were prepared.•Ln-CP 1 shows good catalytic reactivity and selectivity for the Strecker reaction.•Ln-CP 1 exhibits sensitive fluorescent response to Cu2+ in DMF solution.Two new isostructural lanthanide coordination polymers (Ln-CPs) [Ln2(bpdc)3(DMF)2] (Ln = Tb for 1, Eu for 2) with two kinds of one-dimensional channels along the a axis, were synthesized by 2,2′-bipyridyl-4,4′-dicarboxylic acid (H2bpdc) under solvothermal conditions. With exposed Lewis acid Ln3+ centers, 1 as a heterogeneous catalyst shows good catalytic reactivity and selectivity for the Strecker reaction affording medium to excellent conversion yields. Luminescent studies illustrate that 1 and 2 show intensive green and red luminescence triggered by efficient antenna effect of ligands under UV light, respectively. Moreover, 1 exhibits sensitive fluorescent response to Cu2+ in DMF solution.For 3D isostructural LnCPs [Ln2(bpdc)3(DMF)2] (Ln = Tb for 1, Eu for 2), 1 as a heterogeneous catalyst shows good catalytic reactivity and selectivity for the Strecker reaction affording medium to excellent conversion yields. In addition, 1 exhibits sensitive fluorescent response to Cu2+ in DMF solution.

Indium metal–organic frameworks (MOFs) were first used as recyclable heterogeneous Lewis acid catalysts for the synthesis of amino acid derivatives with excellent conversion yields. Moreover, exposed ether groups (Lewis basic sites) on the pore walls of In-MOF 2 could activate trimethylsilyl cyanide, forming hypervalent silicate intermediates, as proven by 29Si NMR.

By reaction of 3,3′,5,5′-biphenyltetracarboxylic acid (H4BPTC) with various lanthanide ions, seven novel three dimensional (3D) lanthanide metal–organic frameworks (MOFs) have been prepared under solvothermal conditions, namely, [Ln3(BPTC)3(H2O)2]·3H3O·4H2O·3DMF (DMF = N,N-dimethylformamide, Ln = Eu (1), Tb (2), Sm (3) Dy (4)), [Nd(BPTC)(H2O)2]·H3O·DMF (5), [Er2(BPTC)(HCOO)3(H2O)2]·(CH3)2NH2 (6), and [Tm12(BPTC)8(HCOO)11(H2O)10]·10DMF·7(CH3)2NH2 (7). Combining different lanthanide ions and diversity of coordination modes of the H4BPTC ligand, the seven compounds display interesting structural characteristics. Of these, compounds 1–4 are isostructural and demonstrate a unique 3D coordination framework containing two types of 1D channel, that is built by the novel trinuclear [Ln3O22] SBUs. Compound 5 can be described as a new 3D open-framework structure with quadrilateral-shaped 1D channels based on [Nd2O16] SBUs. Compound 6 has a new 3D pillar network feature constructed by trapezoidal chains linked by bridging BPTC4− ligands, whilst compound 7 exhibits a 3D network with a number of rare oval-shaped channels along the [101] direction. The H4BPTC ligand exhibits five new coordination modes, which are firstly reported in M-BPTC frameworks. Compounds 1–7 all display their typical emission bands upon irradiation at the ligand band at room temperature. Compounds 1–4 present strong characteristic emissions in the visible region, of which compounds 1 and 2 show millisecond luminescence lifetimes. The NIR photoluminescent of lanthanide MOFs is less well observed, especially for the Tm(III) compounds. Owing to the good sensitization of the H4BPTC ligand, compounds 5–7 display near-infrared region (NIR) emission with microsecond luminescence lifetimes. In addition, compounds 2, 5, 6 and 7 exhibit global antiferromagnetic behaviors, of which compound 5 shows a weak ferromagnetic coupling at 235 K.

•Two novel 3D open-framework gallium phosphites have been synthesized.•Right- and left-handed helical chains construct the 3D framework.•Both compounds show low framework density.Two new 3D open-framework gallium phosphites Ga(HPO3)F2·(H2A)0.5, where A = C5N2H12(1) and C6N2H14 (2) have been solvothermally synthesized in the presence of 2-methyl piperazine and N,N′-dimethyl piperazine as template, respectively. Single crystal X-ray diffraction reveals that these two compounds have the similar inorganic framework structures, which may be viewed as the assembly of a second building unit (SBU), Ga2F2O4(HPO3)2 containing one dimer Ga2F2O8 and two HPO3 groups. The SBUs are linked with each other via vertex-sharing oxygen atoms to form a new 3D open-framework which possesses the left- and right-handed helical chains along c axis. With the SBU as 4-connected nodes, the structure can be simplified into a uninodal NbO topology. Moreover, compounds 1 and 2 show low framework density value of 9.4 and 9.7, respectively. Crystal data: compound 1, Trigonal, R-3 (148), a = b = 18.315(3) Å, c = 13.136(4) Å, γ = 120°, V = 3815.9(13) Å3 and Z = 9; compound 2, Trigonal, R-3 (148), a = b = 17.8476(4) Å, c = 13.5159(6) Å, γ = 120°, V = 3728.5(2) Å3 and Z = 18.

•Two new CPs have been prepared by rigid 1,3-H2adc ligand.•1 features a 1D zigzag chain containing the dimeric [Ni2Cl2(2,2′-bipy)2]2+ units.•2 shows a 2D layer with the rhombic windows built from the infinite bent Pb–O chains.•1 shows a high thermal stability limit of 425 °C.•1 displays the ferromagnetism in the range of 4–300 K.Two new metal coordination polymers (CPs) based on rigid 1,3-adamantanedicarboxylic acid (1,3-H2adc) ligand have been successfully prepared under different solvothermal conditions. In these two compounds, Ni2Cl2(2,2′-bipy)2(1,3-adc) (1) (2,2′-bipy = 2,2′-bipyridine) and Pb(H2O)(1,3-adc) (2), 1,3-adc2− ligand displays two different coordination modes, constructing disparate architectures by bridging the different building units. Compound 1 features a chiral 1D zigzag chain containing the dimeric [Ni2Cl2(2,2′-bipy)2]2+ units and 1,3-adc2− bridging ligands. The zigzag chain and its enantiomer alternately stack along the a axis through the π–π stacking interactions of bipy ligands. Compound 2 shows a 2D layer with the rhombic windows built from the infinite bent Pb–O chains and 1,3-adc2− bridging ligands. Moreover, compound 1 shows a high thermal stability limit of 425 °C and displays ferromagnetic interactions in the range of 4–300 K.Two new CPs based on rigid 1,3-H2adc ligand have been prepared under different solvothermal conditions. 1,3-adc2− displays two different coordination modes, constructing disparate architectures by bridging the different building units. Ni–CP shows the ferromagnetism in the range of 4–300 K.

•A new In(III) coordination polymer was prepared by 1,4-bdc ligand.•It possesses a 3D framework with the square-shaped channels.•It exhibits good catalytic ability for cyanosilylation of aromatic aldehyde.•The catalyst can be reused three times without losing activity or significant mass.A new indium coordination polymer, In(OH)(H2O)(1,4-bdc) (1,4-H2bdc = 1, 4-benzendicarboxylic acid), has been prepared under solvothermal conditions using a mixture of rigid organic linker and inorganic heteropolyacid (12-phosphotungstic acid) template. Single-crystal X-ray diffraction analysis reveals that this new compound possesses a 3D framework with the square-shaped channels constructed from the infinite indium-oxide chains and rigid 1,4-bdc ligands. This compound exhibits good catalytic activity for the cyanosilylation of aromatic aldehydes and can be reused three times without losing activity or significant mass.A new 3D indium coordination polymer In(OH)(H2O)(1,4-bdc) with the square -shaped channels has been prepared under solvothermal conditions. It exhibits good catalytic activity for the cyanosilylation of aromatic aldehydes and can be reused three times without losing activity or significant mass.

•Two new In(III) CPs with different 2D layer structures were synthesized.•Non-classical hydrogen-bonds link 2D entities to 3D frameworks.•They show strong fluorescence emission with long lifetime.Two indium coordination polymers (CPs) with different structures InCl(2,6-pdc)(H2O) (1) and In2Cl4(2,6-pdc)(4,4′-bipy)2 (2) were synthesized by the reactions of InCl3 with 2,6-pyridinedicarboxylic acid (2,6-H2pdc) and 4,4′-bipyridine (4,4′-bipy) ligands. Compound 1 features a two dimensional (2D) network with the rhombic windows constructed from novel [In2O6(H2O)2Cl2(2,6-pdc)2] dimeric building units and 2,6-pdc2− ligands. Compound 2 possesses a 2D layer structure which is accomplished by connecting the wavy chains to the distorted 4,4′-bipy ligands. The different structures of 1 and 2 show the predominant influence of chlorine atoms and organic ligands. In addition, non-classical hydrogen-bond (C–H⋯Cl) interactions also play an important role in the formation of supramolecular architectures, for instance, to link 2D entities to 3D frameworks. These new In(III) CPs show intense fluorescence emission with long lifetimes in the solid state at room temperature.

A new chiral open-framework indium phosphite In3(HPO3)6(H3DETA)·2H2O 1 has been synthesized under hydrothermal conditions using achiral diethylenetriamine (DETA) as template and characterized by single crystal X-ray diffraction, powder X-ray diffraction, IR spectroscopy, TGA, ICP–AES and elemental analyses. Single crystal X-ray diffraction analysis reveals that the 3D inorganic framework is built up by alternation of InO6 octahedra and HPO3 pseudo-pyramids. Interestingly, the right-handed inorganic helical ribbons are presented in the 3D open-framework while fascinating hydrogen-bonded helices are self-assembled under hydrothermal conditions between organic template molecules and H2O molecules. It is worth noting that the guest hydrogen-bonded helical chain and the host helical ribbon of inorganic framework show the same chirality and intertwine with each other along the b axis. Further understanding of the hydrogen bonds between guest molecules and inorganic framework demonstrates that the flexible DETA molecule may conduce to the formation of the chiral framework. Crystal data: In3(HPO3)6·(H3DETA)·2H2O, Monoclinic, P21 (No. 4), a = 9.2713(19) Å, b = 14.453(3) Å, c = 9.996(2) Å, β = 116.16(3)°, V = 1202.2(4) Å3, and Z = 2, Flack parameter: 0.0(4).Graphical abstractHighlights► It is the first main group metal phosphite with chiral open-framework structure. ► It possesses special intertwined host helical ribbons and guest helical chains. ► The hydrogen bonds play an important role in the formation of the chiral framework.

Two new indium MOFs based on rigid 1,4-naphthalenedicarboxylate (1,4-NDC) ligand have been successfully prepared under different solvothermal conditions and characterized by single crystal X-ray diffraction, powder X-ray diffraction, IR spectroscopy, TGA, elemental analyses and luminescence spectrum. In these two compounds, In(OH)(1,4-NDC)·2H2O (1) and HIn(1,4-NDC)2·2H2O·1.5DMF (2), (DMF = N, N′-dimethylformamide), 1,4-NDC exhibits two different coordination modes, constructing disparate architectures by bridging the different building units. Compound 1 exhibits a 3D framework with two kinds of square shape channels that built up from the infinite chains of corner-sharing In(OH)2O4 octahedra with 1,4-NDC ligands. Compound 2 possesses a 3D anion framework with twofold interpenetrating diamond topology which is accomplished by connecting four linear 1,4-NDC ligands to the four-connected In(III) nodes. Moreover, compounds 1 and 2 exhibit strong solid-state luminescence emissions at room temperature.Graphical abstractHighlights► Two new porous In-MOFs are synthesized based on same rigid carboxylate ligand. ► Solvent plays an important role on the formation of In-MOFs. ► Two In-MOFs exhibit strong solid-state luminescence emissions at room temperature.

A novel porous chiral In-MOF InH(D-C10H14O4)2 (1) with a left-handed helical channel assembled from D-(+)-camphoric acid (D-H2Cam), has been prepared under solvothermal conditions. Single-crystal X-ray diffraction analysis reveals that compound 1 crystallizes in the tetragonal space group P43212 (no. 96) with parameters: a = 13.8954 Å, b = 13.8954 Å, c = 17.7870 Å, V = 3434.4(7) Å 3, Z = 4. The framework feature of compound 1 is characteristic of four-connected anionic-type diamond net with left-handed chiral channel. Moreover, compound 1 exhibits high surface area.

A new 2D layered gallium phosphite Ga(HPO3)F3·(trans-C6N2H16) 1, possessing left- and right-handed helical chains, has been solvothermally synthesized in the presence of 1,2-diaminocyclohexane (DACH) as a structure-directing agent. The inorganic framework of compound 1 consists of [Ga2O4F6] dimers and HPO3 groups. The dimers are linked up via HPO3 groups to give rise to left- and right-handed helical chains along the b-axis, further these two types of helical chains are alternately connected, with [Ga2O4F6] dimer units functioning as hinges to form a novel 2D layered network in the bc-plane. Interestingly, although a mixture of cis and trans isomers of DACH are used in the synthesis, only the trans isomer is found to direct the formation of compound 1. Moreover, the chirality of the racemic trans isomers of DACH can be transferred into the inorganic framework by hydrogen-bond. The crystal data are as follow: Ga(HPO3)F3·(trans-C6N2H16); M = 322.91; Monoclinic; P21/c (14); a = 11.2635(5) Å; b = 9.8212(5) Å; c = 10.1458(3) Å; β = 102.981(2)°; Z = 4.

Two new three-dimensional indium phosphite and indium phosphite–phosphate [In3(H2PO3)3(HPO3)4]·(trans-C6N2H16) 1 and [In6(HPO3)8(H2PO3)5(H2PO4)]·(C3N2H12)22 have been synthesized under hydrothermal conditions using 1,2-diaminocyclohexane (1,2-DACH) and 1,3-diaminopropane (1,3-DAP) as structure directing agents, respectively and further characterized by powder X-ray diffraction, single crystal X-ray diffraction, IR spectroscopy, TGA, ICP-AES and elemental analyses. These two compounds have the similar 3D inorganic framework structures with intersecting 8-membered ring (8-MR) channels. In compound 1, the diprotonated trans-1,2-DACH cations occupy the 8-MR channels along the [0 0 1] direction even though a mix of trans- and cis-isomers of 1,2-DACH molecules are added in the reaction mixture. Moreover, the chirality of trans-1,2-DACH alternates along the channels. It is noted that compound 2 is the first indium phosphite–phosphate compound. Crystal data: compound 1, monoclinic, C2/c (No. 15), a = 18.675(4) Å, b = 10.220(2) Å, c = 13.419(3) Å, β = 98.29(3)°, V = 2534.4(9) Å3, and Z = 4. Compound 2, orthorhombic, Pna21 (No. 33), a = 26.7974(9) Å, b = 9.8459(3) Å, c = 18.5441(6) Å, V = 4892.8(3) Å3, and Z = 4.

A novel lanthanide metal–organic framework, [Eu2(BDC)3(DMF)2]·(DMF)1.7(BDC = 1,3-benzenediacarboxylate) 1 has been synthesized under solvothermal condition and characterized by single-crystal X-ray structure determination, luminescent property, nitrogen gas adsorption, powder X-ray diffraction, IR, and TGA.[Eu2(BDC)3(DMF)2]·(DMF)1.7 has one-dimensional hexagonal channels and high thermal stability. Moreover, it emits red light in solid state at room temperature and has good adsorption property of nitrogen gas.

In this work, we present a rare earth metal–organic framework, Y2(H2O)(BDC)3(DMF)]·(DMF)3 (BDC = 1,3-benzenedicarboxylate) 1, with a rare 2D (42.6)(45.6)2(48.62)(49.65.8) net, helical tubes with opposite chirality interweaving of triple-helical chains, opened windows and high thermal stability.Y2(H2O)(BDC)3(DMF)]·(DMF)3 has a rare 2-D (42.6)(45.6)2(48.62)(49.65.8) net, helical tubes with opposite chirality interweaving of triple-helical chains, opened windows and high thermal stability.

A new metal–organic framework [In2(OH)2(1,3-BDC)2(2,2′-bipy)2] 1 (1,3-benzenedicarboxylate = 1,3-BDC, 2,2′-bipyridine = 2,2′-bipy) has been hydrothermally synthesized from the reaction of In(NO3)3, 1,3-BDC and 2,2′-bipy. Single-crystal X-ray diffraction analysis reveals that compound 1 crystallizes in the triclinic space group P-1 (No. 2), a = 8.6461 Å, b = 9.9234 Å, c = 10.1799 Å, α = 78.1801°, β = 75.1646°, γ = 72.7427°, V = 798.40 Å3, Z = 2. Compound 1 contains double-chain-like ribbons which are constructed by In2(OH)2(2,2′-bipy)2∞2+ units and 1,3-BDC ligands. The adjacent ribbons are packed and exhibit interesting 3D supramolecular networks. The further characterizations of compound 1 have been performed by fluorescent spectroscopy, powder X-ray diffraction, IR spectroscopy, thermogravimetric analysis (TGA), ICP-AES and elemental analyses.

A new open-framework gallium phosphite Ga5(OH)2(HPO3)8(C4N3H16) · 2H2O (1) is synthesized solvothermally using diethylenetriamine (DETA) as template from a mixed solvent system in which ethylene glycol (EG) was used as the co-solvent. The as-synthesized product is characterized by single crystal X-ray diffraction, powder X-ray diffraction, IR spectroscopy, thermogravimetric analysis (TGA), ICP-AES and elemental analyses. The three-dimensional open-framework of compound 1 is constructed from two novel secondary building units (SBUs), Ga2O7(OH)(HPO3) three-membered ring (3R) and Ga(HPO3)6 tooth-wheel type unit. These two novel secondary building units are first found in gallium phosphate/phosphite, which lead to form the one-dimensional 8-membered ring channels along the a-axis. Moreover, it is noted that compound 1 is the first gallium phosphite containing 5-fold coordinate gallium atom.The 3D open-framework of compound 1 with 1D 8-membered ring channels along the a-axis which is constructed from two novel secondary building units (SBU), three-membered ring Ga2O7(OH)(HPO3) and tooth-wheel type unit Ga(HPO3)6.

Two new metal-organic materials, In(2,2′-bipy)(btec)0.5Cl (1) and In2(phen)4(Hbtec)2 (2) (btec = 1,2,4,5-benzenetetracarboxylate, 2,2′-bipy = 2,2′-bipyridyl, phen = 1,10-phenanthroline) have been synthesized under mild hydrothermal condition. Their structures were determined by single-crystal X-ray diffraction and further characterized by X-ray powder diffraction, thermogravimetric analysis, IR, fluorescence spectroscopy, inductively coupled plasma (ICP) and elemental analysis. The structural analysis reveals that compound 1 exhibits a novel wavelike 2D layer with unusual contorted rhombic grids, while compound 2 possesses dinuclear In2(phen)4(Hbtec)2 complex molecules. It is noteworthy that their structures finally extend to the higher dimensional supramolecular framework structures through the π–π stacking interactions of N-donor ligands. Additionally, these two compounds show strong fluorescence in the solid state at room temperature.Two new metal-organic materials, In(2,2′-bipy)(btec)0.5Cl (1) and In2(phen)4(Hbtec)2 (2) have been synthesized under mild hydrothermal condition. Compound 1 exhibits a novel wavelike 2D layer with unusual contorted rhombic grids, while compound 2 possesses dinuclear In2(phen)4(Hbtec)2 complex molecules. Their structures finally extend to the higher dimensional supramolecular framework structures through the π–π stacking interactions of N-donor ligands. Additionally, these two compounds show strong fluorescence in the solid state at room temperature.