A new multistimuli-responsive luminescent material, [Cu8I8(4-dpda)6]n (1) (4-dpda=4-(diphenylphosphino)-N,N-dimethylaniline), has been obtained by combining inorganic Cu8I8 clusters and organic ligands 4-dpda, providing a novel in-/organic hybrid approach as an interesting alternative to all-organic approaches. Compound 1 responds well to thermo and mechanical force independently with color change due to the fact that the stimuli affect frontier molecular orbital and molecular packing modes, respectively.

Reactions of the semirigid polycarboxylate ligand, 2-aminodiacetic terephthalic acid (H4adtp), with Zn(II) and Cd(II) salts resulted in {[Zn2(adtp)(H2O)2]·2H2O}n (1) and [Cd2(adtp)(μ2-H2O)(H2O)3]n (3), respectively. By introducing auxiliary ligand 4,4′-bipyridine (bpy), two 3D regularly arranged pillared-layered frameworks {[Zn3(adtp)(bpy)1.5(μ3-OH)(H2O)]·NO3·3H2O}n (2a) and {[Cd4(adtp)2(bpy)(H2O)4]·2.5H2O}n (4) were obtained. Complex 1 is characterized as a two-dimensional (2D) layer structure, whereas complex 3 features a three-dimensional (3D) framework with two types of alternately arrayed channels. In complex 2a, the one-dimensional (1D) zinc chains built up of alternately interlinked tetranuclear and dinuclear units are cross-linked into 2D layers, which are further pillared by bpy into a 3D cationic framework with NO3− as counterions. As for 4, a 3D pillared-layer framework is observed and comprises carboxylic μ2-O bridged –M–O–M– chains. The auxiliary ligand bpy exerts a structure-directing effect on the resultant 3D pillared-layer architectures in 2a and 4, wherein μ3-OH bridged tetranuclear metal units or carboxylic μ2-O bridged –M–O–M– chains appear. Additionally, the cationic framework in 2a is strongly dependent on counter anions and the concentration of bpy ligand. The isomorphic {[Zn3(adtp)(bpy)1.5(μ3-OH)(H2O)]·ClO4·3H2O}n (2b) with ClO4− as template and counterions is also obtained. The luminescent properties of 1, 2a, 3 and 4 are investigated in detail. Compared with free H4adtp, complex 3 exhibits a larger blue-shifted emission band. Complex 2a displays tunable photoluminescence by variation of excitation light and temperature due to multi-centers emissions.

A series of novel two-dimensional (2D) lanthanide coordination polymers with 4-hydroxyquinoline-2-carboxylate (H2hqc) ligands, [Ln(Hhqc)3(H2O)]n·3nH2O (Ln = Eu (1), Tb (2), Sm (3), Nd (4), and Gd (5)) and [Ln(Hhqc)(ox)(H2O)2]n (Ln = Eu (6), Tb (7), Sm (8), Tm (9), Dy (10), Nd (11), Yb (12), and Gd (13); H2ox = oxalic acid), have been synthesized under hydrothermal conditions. Complexes 1–5 are isomorphous, which can be described as a two-dimensional (2D) hxl/Shubnikov network based on Ln2(CO2)4 paddle-wheel units, and the isomorphous complexes 6–13 feature a 2D decker layer architecture constructed by Ln-ox infinite chains cross-linked alternatively by bridging Hhqc– ligands. The room-temperature photoluminescence spectra of complexes EuIII (1 and 6), TbIII (2 and 7), and SmIII (3 and 8) exhibit strong characteristic emissions in the visible region, whereas NdIII (4 and 11) and YbIII (12) complexes display NIR luminescence upon irradiation at the ligand band. Moreover, the triplet state of H2hqc matches well with the emission level of EuIII, TbIII, and SmIII ions, which allows the preparation of new optical materials with enhanced luminescence properties.

Treatment of bix (1, 4-bis(imidazole-1-ylmethyl)benzene) with AgI generated [(Ag4I4)(bix)]n1, whose crystal structure reveals a 2D organic–inorganic layer formed by novel wave-like silver(I) iodide chains with the linkers of bix ligands. The layers are arranged in parallel with the mode of {ABAB…} type showing 1D rectangular channels. In solid state, 1 exhibits multiple emission properties originating from its different natures, while optical absorption spectrum suggests that 1 might be a potential wide-gap semiconductor.A 2D organic-inorganic layer structure [(Ag4I4)(bix)]n (1) (bix=1,4-bis(imidazole-1-ylmethyl)benzene) was reported, which formed by novel wave-like silver(I) iodide chains with the linkers of ligands. The layers are arranged in parallel with the {ABAB…} mode showing 1D rectangular channels. 1 exhibits multiple emissions properties originating from its different natures.Highlights► A 2D organic–inorganic layer based on novel wave-like silver(I) iodide chains. ► The layers are arranged in parallel with the mode of {ABAB…} type showing 1D rectangular channels. ► Exhibiting multiple emissions properties originating from its different natures.

Complexes [Zn(bpdc)(H2O)2] (1) and [Mn(bpdc)(H2O)3]∙2.5H2O (2) were assembled by 2,2′-bipyridine-6,6′-dicarboxylate (H2bpdc) with Zn2+ or Mn2+ under hydro/solvo-thermal conditions. Complexes 1 and 2 are extended from mononuclear to 1D, 2D and 3D supramolecular network step by step with the help of intramolecular weak interactions. The luminescent properties of 1 had been investigated in details, which show intense blue emission with relatively good quantum yield. The 2 displays nonlinear optical (NLO) activity comparable with that of KDP, and exhibits weak antiferromagnetic coupling between the Mn (II) ions by the hydrogen bonds.Compound 1 display intense blue luminescence and 2 revealed NLO response and antiferromagnetic coupling. Both of them extend from mononuclear to 3D supramolecular network by the intermolecular interactions.Highlights► The two mononuclear complexes are assembled by 2,2′-bipyridine-6,6′-dicarboxylate. ► The intense blue fluorescence of 1 originates from MLCT. ► 2 crystallizes in acentric space group and shows NLO activity. ► The antiferromagnetic coupling of 2 caused by hydrogen bonds.

A series of novel three-dimensional (3D) 3d-4f heterometallic coordination complexes, [{LnZn(bpdc)2(OAc)(H2O)2}·H2O]n (Ln = Nd (1), Sm (2), Eu (3), Tb (4), Dy (5), Er (6); H2bpdc = 2,2′-bipyridyl-4,4′-dicarboxylic acid; HOAc = acetic acid), have been successfully synthesized under hydrothermal conditions and characterized by single-crystal X-ray diffraction. All complexes are isostructural and display new 2-fold interpenetrating (3,6)-connected network topology. The luminescent properties of 1–5 in the solid state at room temperature have been studied in detail. It is the first series of luminescent 3d-4f heterometallic complexes with bpdc2– ligands, and it has been found that the energy transitions from the ligands to Eu3+ and Tb3+ are more effective than those to Sm3+ and Nd3+, and the energy transition from the ligand to Dy3+ is in between. Furthermore, thermogravimetric analysis and powder X-ray diffraction are also investigated.

Five MnII-sdba coordination polymers with mono-, di-, tri-, tetra-nuclear cores based on the V-shaped 4,4′-dicarboxybiphenyl sulfone (H2sdba) ligands: [Mn(sdba)(phen)2(H2O)]n·3nH2O (1), [Mn2(sdba)2(μ-H2O)(py)4]n (2), [Mn3(sdba)2(Hsdba)2(2,2′-bipy)2]n (3), [Mn4(sdba)4(4-mepy)2(H2O)4]n·2nH2O (4) and [Mn4(sdba)4(bpp)4(μ-H2O)2]n·0.5nH2O (5) (phen = 1,10-phenanthroline, 2,2′-bipy = 2,2′-bipyridine, 4-mepy = 4-picoline, bpp = 1,3-bi(pyridine-4-yl)propane) were hydrothermally synthesized and structurally characterized. The M–O–C metal clusters in above complexes act as SBUs, and the V-shaped sdba ligands link the SBUs to generate the novel frameworks. In complexes 1 and 3 their 1D chains are linked into the 2D planes through various hydrogen bonding. Complex 2 displays the 3D structure with interpenetrated threefold, while complexes 4 and 5 both exhibit the 3D structures with the tetra-nuclear Mn4 units. The magnetic susceptibility studies in the 2–300 K range for these complexes reveal the existence of anti-ferromagnetic exchange interactions between the MnII ions.Five MnII-sdba coordination polymers with mono-, di-, tri-, tetra-nuclear cores based on the V-shaped 4,4′-dicarboxybiphenyl sulfone (sdba) were reported. These complexes display the 2D or 3D structures with interpenetrated threefold or the tetra-nuclear Mn4 units. The magnetic susceptibility studies in the 2–300 K range for these complexes reveal the presence of anti-ferromagnetic exchange interactions between the MnII ions.

A novel luminescent inclusion complex, {[(C4AS)2Ag3(μ-2,2′-bpy)2(2,2′-bpy)2] [Ag5(μ-2,2′-bpy)4(2,2′-bpy)4]·20H2O}n (1) (2,2′-bpy = 2,2′-bipyridine, C4AS = p-sulfonatocalix[4]arene), with an unusual framework is reported: the parallel 1D infinite silver(I) chains separated by the water belts reside in the big cavities of the p-sulfonatocalix[4]arene-trisilver blocks.

Three d10−d10 transition-metal complexes with organosulfur ligands, Cu6(btt)6 (1), Cu4(btt)4 (2), and Ag6(bmt)6·6THF (3) (Hbtt = 2-benzothiazolethiol, Hbmt = 2-benzimidazolethiol, and THF = tetrahydrofuran), were synthesized and characterized. Complexes 1 and 2 with similar coordination environments are isomers crystallized from the same solvothermal reactions, but they cause great differences in both the structures and luminescent behaviors. The hexanuclear cluster 1 exhibits unusual near-infrared luminescence and high thermal stability, while complex 2 with tetranuclear cores and stronger metal−metal bonds shows an intense red emission like that from complex 3.

The reactions of 2,4,6-tri(2-pyridyl)-1,3,5-triazine (tpt) and Ag(I) ions under solvothermal or solvent evaporation conditions yielded three new coordination complexes with the interesting frameworks: [Ag(tpt)(NO3)]n (1), [Ag2(tpt)(NO3)(PPh3)2(H2O)](NO3)·2H2O (2), [Ag8(tpt)4(NO3)4(µ2-CN)2](NO3)2 (3) (PPh3= triphenylphosphine). Complex 1 crystallizes in a chiral space groupP212121, giving a 1D chain and left-handed helical structure which is the first example of metal-tpt complexes with helical chains. Through the π–π interactions and C–H⋯O hydrogen bonding, the 1D chains of 1 further form a 3D supramolecular structure. Dinuclear complex 2 gives a 3D network via intramolecular O–H⋯O and C–H⋯O hydrogen bonding, while the octanuclear complex 3 affords a 2D framework through weak Ag⋯Ag interactions and van der Waals force. Complexes 1 and 3 exhibit high thermal stabilities at 350 and 300 °C, respectively, and both display unusual yellow luminescence in the crystal-state at cryogenic temperature.

A new mixed-valence hexadecavanadate cluster compound, (Me2NH2)4[H6V16O42(SO4)] · 8H2O (1), has been synthesized via an efficient method in organic media. The hollow cluster shell of 1, with a sulfate ion locating in its centre, exhibits four large eight-membered –O–V–O–V– rings on its surface, which makes the cluster into a half-open structure distinguished from the common hollow clusters built up with closed surfaces. The intense blue luminescence of 1 in solution state is scarcely reported for the polyoxometalate clusters.A new mixed-valence hexadecavanadate cluster compound, (Me2NH2)4[H6V16O42(SO4)] · 8H2O (1), has been synthesized via efficient method in organic media. The hollow cluster shell of 1, with a sulfate ion locating in its centre, exhibits four large eight-membered –O–V–O–V– rings on its surface, which makes the cluster into a half-open structure.

Two coordination polymers, [In(btc)(2,2′-bpy)(H2O)]n · nH2O (1) and [In2(btec)(2,2′-bpy)2Cl2]n (2) (H3btc = 1,3,5-benzenetricarboxylic acid, H4btec = 1,2,4,5-benzenetetracarboxylic acid, 2,2′-bpy = 2,2′-bipyridine), have been prepared under hydrothermal conditions. Single-crystal X-ray diffraction analyses reveal that compounds 1 and 2 consist of two-dimensional double layer structures with (3, 3) grids and (4, 2) grids, respectively. The grids along two different directions in 1 are of the opposite chirality, while the interactions of double-layer sheets in 2 create a three-dimensional supramolecular network with one-dimensional tunnels. The additional green luminescences for both 1 and 2 in the solid state at low temperature imply the red shift of emission energy in the compounds, which may derive from LMCT. Their X-ray powder diffractions and thermogravimetric analyses are also discussed.Two coordination polymers, [In(btc)(2,2′-bpy)(H2O)]n · nH2O (1) and [In2(btec)(2,2′-bpy)2Cl2]n (2), prepared under hydrothermal condition consist of two-dimensional double layer structures with (3, 3) grids and (4, 2) grids, respectively. The grids along two different directions in 1 are of the opposite chirality, while the interactions of double-layer sheets in 2 create a three-dimensional supramolecular network with one-dimensional tunnels. Their additional green luminescences at low temperature imply the red shift of emission energy in the compounds, which may derive from LMCT. The X-ray powder diffractions and thermogravimetric analyses are also discussed.

Two 3d−4f heterometallic coordination polymers [EuCo(pydc)3(H2O)3]n · 2nH2O (1) [YbCo(pydc)3(H2O)3]n · nH2O (2) have been hydrothermally synthesized from pyridine-2,4-dicarboxylic acid (H2pydc). Compounds 1 and 2 possess isostructural twofold interpenetration corrugated brick wall layer structures with (6,3) topology.Two 3d−4f heterometallic coordination polymers [EuCo(pydc)3(H2O)3]n · 2nH2O (1) [YbCo(pydc)3(H2O)3]n · nH2O (2) have been hydrothermally synthesized from pyridine-2,4-dicarboxylic acid (H2pydc). Compounds 1 and 2 possess isostructural twofold interpenetration corrugated brick wall layer structures with (6,3) topology.

Single crystals of [W11Ni1P1O39(Hbpy)](H2bpy)2 · 4.25H2O (1) and (W11Zn1P1O39)(H2bpy)2(Hbpy) · 1.5H2O (2) have been hydrothermally synthesized at 160 °C and both characterized by IR, elemental and single-crystal structural analyses. Compound 1 has a ladder-like chain structure by hydrogen bonding interactions, whereas 2 contains an unprecedented chain of Keggin polyoxotungstates by oxo-bridges and form a 2-D layer via hydrogen bonds.

Assembly of InCl3 with 1,3,5-benzenetricarboxylic acid (H3btc) and pyridine or pyridine derivatives under hydrothermal conditions produces a series of isostructural coordination polymers with the interesting frameworks: {(HL)[In4(OH)4(btc)3]·L·3H2O}n, L=pyridine (1); L=2-picoline (2); L=4-picoline (3) and {(Hdpea)[In4(OH)4(btc)3]·3H2O}n (4) (dpea=1,2-di(4-pyridyl)ethane). In these four complexes, carboxyl and hydroxyl oxygen atoms bridge indium(III) centers to form octahedral chain-like sinusoidal curves, which are further interlinked by btc3− moieties to generate 3-D frameworks with 1-D channels. The protonated guests HL in 1–3 located at the channels can be fully exchanged by K+ ion or partially exchanged by Sr2+, and Ba2+ ions.Four In(III)-btc isostructural polymers with 3-D channel frameworks formed from octahedral chain-like sinusoidal curves and layers interlinking. The guests pyridine and its derivatives at channels can be exchanged by K+, Sr2+ and Ba2+ ions.

A novel luminescent inclusion complex, {[(C4AS)2Ag3(μ-2,2′-bpy)2(2,2′-bpy)2] [Ag5(μ-2,2′-bpy)4(2,2′-bpy)4]·20H2O}n (1) (2,2′-bpy = 2,2′-bipyridine, C4AS = p-sulfonatocalix[4]arene), with an unusual framework is reported: the parallel 1D infinite silver(I) chains separated by the water belts reside in the big cavities of the p-sulfonatocalix[4]arene-trisilver blocks.