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By tuning the reaction solvents, two 3D luminescent MOFs based on Cu3I3S clusters, {[Cu3I3(TPSA)]·DEF}n (1) and {[Cu3I3(TPSA)]·DMF}n (2), have been obtained by utilization of a conformationally flexible ligand N,N′,N′′-tri(3-pyridine)thiotriamide phosphate (TPSA) under solvothermal conditions. They display different fluorescence on account of the proportions between two emission bands, of which, 1 is an orange-yellow-light-emitting phosphor and 2 is a single component white luminescent material. Moreover, the two cluster-based MOFs show multi-stimuli responsive luminescence towards temperature, solvents and nitro explosives.

Three unprecedented multi-cluster copper(i) halides (MCCHs) have been assembled using conformationally flexible ligands. Further explorations demonstrate that the conformational compliance of the ligands may be the key to trap and stabilize the various copper(i)-halide clusters in one system, which opens a new way for the construction of multi-Cu(i)-cluster complexes. Moreover, the MCCHs show distinctive temperature-dependent photoluminescence.

Four lanthanide metal-organic frameworks (Ln-MOFs), namely {[Me2NH2][LnL]·2H2O}n (Ln = Eu 1, Tb 2, Dy 3, Gd 4), have been constructed from a new tetradentate ligand 1-(3,5-dicarboxylatobenzyl)-3,5-pyrazole dicarboxylic acid (H4L). These isostructural Ln-MOFs, crystallizing in the monoclinic P21/c space group, feature a 3D structure with 7.5 Å × 9.8 Å channels along the b axis and the point symbol of {410.614.84} {45.6}2. The framework shows high air and hydrolytic stability, which can keep stable after exposed to humid air for 30 days or immersed in water for seven days. Four MOFs with different lanthanide ions (Eu3+, Tb3+, Dy3+, and Gd3+) ions exhibit red, green, yellow, and blue emissions, respectively. The Tb-MOF emitting bright green luminescence can selectively and rapidly (&lt, 40 s) detect Fe3+ in aqueous media via a fluorescence quenching effect. The detection shows excellent anti-inference ability toward many other cations and can be easily recognized by naked eyes. In addition, it can also be utilized as a rapid fluorescent sensor to detect acetone solvent as well as acetone vapor. Similar results of sensing experiments were observed from Eu-MOF. The sensing mechanism are further discussed.

A series of isostructural coordination polymers based on lanthanide cations and 2,2′-bipyridine-5-carboxylic ligands, i.e. [Ln3L9]n·0.5nH2O (Ln = Eu (1), Gd (2) and Tb (3); HL = 2,2′-bipyridine-5-carboxylic acid), have been synthesized under hydrothermal condition and characterized by single-crystal X-ray diffractions, powder X-ray diffractions (PXRD), thermal analyses (TGA) and elemental analyses (EA). These three complexes all have the 1D chain-like structures containing dinuclear lanthanide units. The solid state luminescent properties of 1 and 3 as well as the magnetic property of 2 are investigated. The results indicate that the 2,2′-bipyridine-5-carboxylic acid ligand is a good sensitizer for the Eu(III) cation.

A one-dimensional (1D) inorganic–organic hybrid based on sandwich-type copper(I)-iodide nanochain was synthesized for the first time. By replacing the copper(I) ions at the sandwich layer with silver(I) ions, a Cu(I)-Ag(I) bimetallic iodide nanochain was isolated. Although they are isostructural, the mixed-metallic one shows a larger band gap and stronger photoluminescence compared with the homometallic one, which may be contributed to the changed valence bands and metallophilic interactions modulated by the silver ions.

Three attractive high-nuclearity neodymium compounds, namely, [Nd10(BSC4A)4(MePO3)4(Cl)2(OH)4(H2O)2(DMF)8(MeOH)2]·3DMF·7CH3OH (1), [Nd11(BSC4A)3(PhPO3)6(Cl)2(OH)6(DMF)12]Cl·7DMF·2CH3OH (2) and [Nd19(BSC4A)5(PhPO3)5(CO3)6(HCOO)7(OH)8(H2O)7(DMF)12]·11DMF·14CH3OH (3), have been solvothermally prepared based on p-tert-butylsulfonylcalix[4]arene (H4BSC4A) and methylphosphonic acid (MePO3H2)/phenylphosphonic acid (PhPO3H2) ligands. Structural analyses reveal that compound 1 features an oval-shaped Nd10 core, where two neodymium ions are in a large 16-membered wheel with –[Nd–O]– repeating units. Compound 2 displays a novel rugby-like Nd11 nanocage housing two μ4-Cl anions, while compound 3 has a large irregular Nd19 core paneled by unexpected carbonato and formate anions generated in situ and represents the highest-nuclearity lanthanide cluster based on the H4BSC4A ligand to date. In addition, the near-infrared luminescence (NIR) and magnetic behaviors of all the title compounds are also investigated.

Two novel microporous metal–organic frameworks were obtained by combination of a tetratopic linker and linear trinuclear cobalt(II) and cadmium(II) cluster subunits. The complexes exhibit unprecedented topological features and unique magnetic and photoluminescence properties.

By utilizing 2-aminodiacetic terephthalic acid (H4adtp) and N-(4-carboxyphenyl)iminodiacetic acid (H34-cpida), two coordination polymers formulated as [Mn(H2adtp)(H2O)]n (1) and [Mn3(4-cpida)2(H2O)2]n (2) have been synthesized under solvothermal conditions without any secondary linker. 1 is a three-dimensional (3D) supramolecular pillar-layered structure, where double hydrogen bonding two H2adtp ligands act as one pillar. 2 is a genuine 3D pillar-layered framework with phenyl moiety as strut. Aminodiacetate functionalities in 1 and 2 demonstrate unprecedented ability in connecting the metal ions into 2D layers. Magnetism studies indicate that two complexes both exhibit dominant antiferromagnetic behaviors. In addition, the fitting of magnetic susceptibility (χM) of 1 is performed based on the model of the alternating –J1J2– coupling chain and considering molecular-field approximation.

Using Cu(NO3)2 as metal salt, [Cu3(cpida)(phen)2(H2O)5]·3NO3·2H2O (1) and {[Cu2(cpida)(phen)(NO3)]·2H2O}n (2a) were synthesized from an identical starting mixture with 2-(carboxyphenyl)iminodiacetic acid (H3cpida) and 1,10-phenanthroline (phen) at 5 °C and 25 °C, respectively. Additionally, complexes 2b–2d, which are isostructural to 2a, were obtained using Cu(ClO4)2, Cu(BF4)2, and Cu(CF3SO3)2 instead of Cu(NO3)2 in the temperature range 0–65 °C. 1 is characterized by a V-shaped trinuclear CuII monomer, whereas 2a–2d features a one-dimensional (1D) Δ CuII chain. Abundant hydrogen bonds constructed by the nitrate anion are observed in 1. A structural transformation study was undertaken and revealed that 1 could completely transform into 2a from the reaction solution at 25 °C and the temperature plays a crucial role in the process. Magnetic measurements revealed that 1 exhibits dominant antiferromagnetic behavior, whereas 2a presents dominant ferromagnetic behavior.

Three new coordination polymers [Zn(Htip)Cl(H2O)]n (1), [Zn(Htip)2]n (2) and [Cd(Htip)2]n·2nH2O (3) were synthesized by reactions of Zn(II)/Cd(II) salts with a multidentate tetrazole-based ligand 2-(4-(tetrazol-5-yl)phenyl)imidazo(4,5-f)(1,10)phenanthroline (H2tip). Complex 1 possesses an infinite 1D coordination chain, and further forms the final 3D supramolecule through π⋯π stacking interactions. Complexes 2 and 3 are isomorphous, and both of them feature an 8-fold interpenetrating 4-connected 3D framework with the dia topological net and the Schlafli symbol of {66}. In 1–3, the Htip− ligand links two metal centers through three terminal N-donors. The structural analyses indicate that the anions and solvents can subtly influence the formation of the resulting network. Moreover, the thermal stabilities and photoluminescent properties of 1–3 are investigated in the solid state.

Two novel decanuclear Ln(III) compounds (Ln = Pr for 1, Nd for 2) have been solvothermally obtained by using p-tert-butylcalix[8]arene (H8TBC8A) and phenylphosphonate (PhPO3H2) as ligands. Single crystal X-ray diffraction studies reveal that both compounds are stacked by dumbbell-like Ln10 clusters, which are capped by two TBC8A8 − supports and linked by four complementary PhPO32 − ligands as well as other bridging anions. In addition, the self-assembly behavior of both compounds is interesting: the cationic Ln10 cluster layers are separated by the layers of H6TBC8A2 − ligands. Moreover, the luminescent and magnetic properties of both compounds were examined.

Utilizing presynthesized large Na2Ni12Ln2 clusters (Ln = Dy and Tb) supported by calixarene as molecular building blocks (MBBs), we have obtained a series of cationic trigonal prismatic heterometallic organic nanocages (HMONCs) with tunable sizes through a stepwise method. Specially, in each structure of the HMONCs, three linear dicarboxylate linkers substitute the peripheral coordinated acetate ligands of two Na2Ni12Ln2 clusters to form an unprecedented Na4Ni24Ln4 HMONC through a M2L3 condensation. Moreover, magnetic study reveals that the Na2Ni12Dy2 core retains its slow magnetic relaxation behavior. Gas sorption behaviors of these HMONCs were also studied. To the best of our knowledge, these HMONCs built from large heterotrimetallic Na2Ni12Ln2 MBBs, which are based on smaller Ni4-calix ones, have not been reported in any other cages to date. In addition, this research also provides a new strategy for the design and construction of HMONCs with predictable structures and functional properties.

In this work, we systematically report four indium–organic framework (InOF) crystals, which comprise the In(CO2)4 monomer for [InCu(inc)4](NO3) (InOF-5) and [Me2NH2]2[In2(Cu4I4)(pdc)4] (InOF-6), the In(OH)(CO2)2 chain for [In2(Cu4I4)(OH)2(nia)4] (InOF-7), and In3O(CO2)6 clusters for [(In3O)2(Cu4I4)3(nia)12(H2O)6](NO3)2 (InOF-8). With the help of the ligand-oriented bifunctional method, a series of novel heterometallic indium–organic frameworks can be easily achieved through the way the pyridyl N-affinitive sites connect to Cu-based units and the COO–-affinitive sites to In(III) centers. This new strategy will open the door to the construction of multifunctional and heterometallic InOF materials.

A series of metal–organic frameworks (MOFs) were systematically synthesized through a solvent-ratio-controlled assembly: {[Et2NH2]2[Zn5(L)2(H2O)4]·2C2H5OH·2H2O}n (1), {[Et2NH2]4[Zn7(HL)2(H2L)2]·4C2H5OH·6H2O}n (2), {[Et2NH2]4[Zn6(L)2(H2L)(H2O)2]·2C2H5OH·2H2O}n (3), {[Et2NH2]4[Zn4(L)2(H2O)2]·4H2O}n (4), and {[Et2NH2]2[Zn2(L)]·C2H5OH}n (5) (H6L = [1,1′;4′,1″]terphenyl-3,5,2′,5′,3″,5″-hexacarboxylic acid, DEF = N,N-diethylformamide). Along with the altering of ratios of the ternary mixed-solvent DEF/H2O/C2H5OH used in the synthetic processes, the coordination modes of the ligand change, which further leads to the different structures of resultant complexes. Owing to diverse metal centers and clusters and distinct ligand coordination modes, these five complexes exhibit totally different and novel topologies: complex 1 displays a (5,8)-connected 3D net, in which the 8-connected nodes are based on trinuclear metal clusters; complexes 2–4 all exhibit 3D 4-nodal nets based on two kinds of metal centers and two kin...

Two novel high-nuclearity manganese clusters, [Mn14(BSC4A)3(tBuPO3)6(μ4-OH)3Cl(H2O)(CH3OH)]·1.5CH3OH (1) and [Mn16(BSC4A)3(PhPO3)7(HPO4)(μ4-OH)3Cl(H2O)(CH3OH)4]·4.5CH3OH (2) (H4BSC4A = p-tert-butylsulfonylcalix[4]arene; tBuPO3H2 = tert-butylphosphonic acid; PhPO3H2 = phenylphosphonic acid) have been solvothermally obtained and structurally characterized. Crystal structural analyses reveal that the phosphonate ligands have a large influence on the structures of the polynuclear manganese clusters: complex 1 possesses a drum-like MnII14 core, which is constructed from three Mn4–BSC4A molecular building blocks (MBBs) and six tBuPO32− ligands and capped by two MnII ions; while complex 2 has a diamond-like MnII16 core, which also consists of three Mn4–BSC4A MBBs, but connected by seven PhPO32− linkers and a tetrahedral Mn4 cluster housing a phosphate anion generated in situ. To the best of our knowledge, complex 2 gives the first calixarene-based cluster linked by both organic phosphonate and inorganic phosphate ligands, and also presents the highest nuclearity manganese complex with the H4BSC4A ligand to date. Magnetic measurements suggest the presence of antiferromagnetic interactions between the adjacent MnII spin carriers for both complexes.

Reactions of the terphenyl-hexacarboxylate ligand [1,1′;4′,1′′]terphenyl-3,5,2′,5′,3′′,5′′-hexacarboxylic acid (H6L) with Zn(NO)3 in the mixed solvents under low-temperature solvothermal conditions afforded five new coordination networks, namely, {[Me2NH2]2[Zn5(L)2(H2O)4]·16H2O}n (1), {[Me2NH2][Zn(H3L)(H2O)]·C2H5OH·5H2O}n (2), {[Me2NH2]2[Zn2(L)(H2O)2]·2DMF·2H2O}n (3), {[Zn4(L)(COO)2(DMF)2(H2O)2]·2C2H5OH·2DMF·2H2O}n (4), and {[Zn4(L)(DMF)4(C2H5OH)(H2O)](OH)2·DMF·2H2O}n (5) (DMF = N,N-dimethylformamide). Compounds 1 and 3–5 possess 3D frameworks, while compound 2 exhibits a 2D grid layer network. Photoluminescence properties of these five compounds have been investigated in solid state at room temperature and low temperature. These five compounds exhibit two kinds of emission modes at room temperature, and compounds 3–5 turn out to have interesting responses to temperature. The sensing properties of compound 1 also have been explored, which show high selectivity and sensitivity to trace amounts of nitrobenzene.

Two attractive Cu(I) coordination polymers with unique structures, namely, {[Cu8(bptp)4]·6H2O} (1) and {[Cu5(bptp)2(CN)]·2H2O} (2), have been successfully synthesized based on a V-shaped multidentate N-containing ligand 2,6-bis[3-(pyrid-4-yl)-1,2,4-triazolyl]pyridine (H2bptp). The structural analysis reveals that complex 1 displays a Cu8 cluster-based infinite 1D ladder chain, in which each H2bptp ligand links four or five Cu(I) ions through nitrogen atoms of pyridine/triazole groups. Complex 2 features an unusual (3,4,5)-connected 3D topological network with the Schlafli symbol (42·54·63·7)(42·63·7)(5·6·8)(5·62·7·82), which has not been reported before. The structural and dimensional diversity of the two complexes indicates that H2bptp exhibits strong coordination ability and diverse coordination modes. It is worth mentioning that the Cu⋯Cu distances in 1 and 2 are shorter than the sum of the van der Waals radii of copper(I) (2.80 A), implying the metal–metal bonding interactions. What is more, the solid-state luminescence bands of 1 and 2 have also been investigated between 298 and 10 K. Interestingly, the low-energy emission bands of 1 and 2 exhibit yellow/orange-red luminescence, and their intensities increase gradually upon cooling.

Five novel Zn(II)/Cd(II) coordination polymers (CPs) based on the V-shaped ligand 1H-3,5-bis(pyrazinyl)-1,2,4-triazole (Hbpt) and different polycarboxylates, {[Cd(bpt)(H2O)]·ClO4·H2O} (1), {[Cd4(bpt)2(suc)2.5(OH)]·3H2O} (2), {[Cd4(bpt)3(1,3-bdc)2.5]·4H2O} (3), {[Cd9(bpt)6(1,4-bdc)6(H2O)2]·4H2O} (4) and {[Zn2(bpt)(H3bhc)(H2O)6]·H2O} (5) (H2suc = succinic acid, 1,3-H2bdc = isophthalic acid, 1,4-H2bdc = terephthalic acid, H6bhc = benzene-1,2,3,4,5,6-hexacarboxylic acid), have been successfully synthesized. Their structures have been characterized using single-crystal X-ray crystallography, powder X-ray diffraction (PXRD) analyses, elemental analyses, IR spectroscopy, and thermogravimetric analyses (TGA). Complex 1 bears a two-dimensional (2D) layered (3,3) network, which is further extended into the resulting three-dimensional (3D) supramolecular architecture via π⋯π stacking interactions between the terminal pyrazine groups of bpt− ligands. In 2, Cd(II) ions and bpt− ligands construct a 2D Cd-bpt layer and two 1D zigzag chains, which are further connected by suc2− ligands to form a 2D + 1D → 3D (4,5)-connected framework. Complex 3 contains two kinds of grids, and their alternating arrangement gives a final complicated 3,4,5-connected network with a stoichiometry of (3-c)6(4-c)9(5-c)2. In 4, the bpt− ligands act as tetradentate ones to connect neighbouring Cd(II) ions into an infinite 1D Cd-bpt chain. The completely deprotonated 1,4-bdc2− ligands further link the adjacent Cd-bpt chains to generate a novel 3,4,6-connected 3D topological network with (3-c)2(4-c)14(6-c). Complex 5 displays an infinite 1D coordination chain. There are strong π⋯π stacking interactions between adjacent chains in 5 with a centroid–centroid distance of 3.860 A and 3.862 A, resulting in a 3D supramolecular structure. The results show that Hbpt can act as a versatile building block for the construction of various coordination polymers. Moreover, the fluorescence properties of 1–5 in the solid state have also been investigated.

Two novel thiacalix[4]arene-based high-nuclearity cobalt clusters, [Na2Co24(BTC4A)6(PO4)6(HCOO)6(DMC)2(DMF)2(dma)4]·5DMF·9CH3OH (denoted as Na2@Co24, 1) and [KCo24(BTC4A)6(PO4)6(Cl)2(HCOO)4(DMF)8][KCo24(BTC4A)6(PO4)6(Cl)2(HCOO)6(DMF)4(CH3OH)2]·8DMF·23CH3OH (denoted as K@Co24, 2) (H4BTC4A = p-tert-butylthiacalix[4]arene, DMC = N,N′-dimethylcarbamic acid anion, dma = dimethylamine), have been solvothermally prepared and structurally characterized. Compounds 1 and 2 are each capped by six Co4-BTC4A molecular building blocks (MBBs) and six phosphate linkers and other different auxiliary anions, possessing an eicositetranuclear Co24 core templated by alkali-metal cations. In essence, compound 1 is templated by two Na+ cations with an attractive interaction in the center of the core, while 2 is templated by one K+ with a larger radius. Such differences “convert” an oval-shaped Co24 disklike core in 1 to a circular core in 2. Interestingly, 2 contains both anionic and cationic KCo24 cores, representing the large...

Five d10 transition-metal clusters, {[Zn15(2,6-Hbptp)(2,6-bptp)7(μ2-O)4(μ2-OH)4(HCOO)2(NO3)(H2O)2]·20H2O} (1), {[Zn8(2,6-Hbptp)(2,6-bptp)5(μ3-O)2]·(ClO4)·7H2O} (2), {[Cd8(2,6-Hbptp)2(2,6-bptp)4(μ3-O)2]·(NO3)2·10H2O} (3), {[Ag7(2,6-Hbptp)(2,6-bptp)3]·4H2O·CH3OH}n (4), and {[Ag6(2,6-Hbptp)2(2,6-bptp)2][Ag6(2,6-Hbptp)2(2,6-bptp)2]2·30H2O·4CH3OH} (5), based on bent ligand 2,6-bis[3-(pyrazin-2-yl)-1,2,4-triazolyl]pyridine (2,6-H2bptp) have been synthesized. Compound 1 exhibits a novel fanlike Zn15 cluster, which is the highest-nuclearity Zn cluster with 2,6-H2bptp reported thus far. In 2 or 3 (M = Zn/Cd), each ligand coordinates to three M2+ ions, to form an M8L6 cluster. The structure of compound 4 is a Ag6 cluster-based 1D chain, where each hexanuclear [Ag6(2,6-Hbptp)(2,6-bptp)3]− cluster links its equivalent ones via sharing the Ag atom. Compound 5 contains two kinds of Ag6 clusters, and the alternating arrangement of them gives the final structure. It is worth mentioning that the Ag–Ag bond distances in 4 ...

A family of high-nuclearity M4n (M = Ni or Co, n = 2–6) coordination nanocages constructed by M4–calix[4]arene molecular building blocks (MBBs) with inorganic phosphate or organic phosphonate ligands have been isolated by solvothermal syntheses and characterized by single-crystal X-ray diffraction. This family can be divided into five structural types with an increase in the number of M4–calix[4]arene MBBs, including Ni8 (1 and 2, n = 2), M12 (M = Ni (3) and Co (4), n = 3), M16 (M = Ni (5) and Co (6), n = 4), Co20 (7, n = 5), and Co24 (8, n = 6) coordination nanocages. Structural analyses reveal that the metallic cores of 1 and 2 are arranged in chair conformation, while compounds 3–6 with closed-shell structures, where their ports are sealed by sodium ions, present the first examples of 2p-3d heterometallic metal–calixarene nanocages to our knowledge. The novel helmet-like Co20 (7) is the only one in this family with an open-shell structure, which can be thought of as a truncated octahedral Co24 (8) nano...

A novel luminescent Ag(I) coordination polymer, [Ag3(cpterpy)2]n·nNO3 (1) (Hcpterpy = 4-(4-carboxyphenyl)-2,2:4′,4-terpyridine), is built-up from Ag(I) ions and terpyridyl-carboxylate ligands with unusual three different coordination modes. The dinuclear [Ag2O2] units with cpterpy- ligands in 1 are linked to form 2D wave-like layers and further connected by [Ag4O6] units into a 3D network, which features 3-fold interpenetrating (3,8)-connected nets with a (41264812)(462)(462) topology. Complex 1 exhibits interesting solid-state photoluminescence and high thermal stability.

Six lanthanide coordination polymers of the formula [Ln(L1)0.5(H2O)2]·2H2O [where Ln3+: Eu3+ (1), Tb3+ (2), and Gd3+(3)] and [Me2NH2][Ln(H2L2)(H2O)4]·0.5DMF·xH2O [where Ln3+: Eu3+ (4), Tb3+ (5), and Gd3+(6)], based on p-terphenyl-2,2″,2‴,5,5″,5‴-hexacarboxylate acid (H6L1), and p-terphenyl-3,2″,3″,5,5″,5‴,-hexacarboxylate acid (H6L2), have been solvothermally synthesized and structurally characterized. Complexes 1–3 are 3D frameworks exhibiting 6-connected pcu alpha-Po primitive cubic network with topology (412.63), while complexes 4–6 show two-dimensional (2D) architectures showing simplified 3,4-connected binodal net and (4.62)(42.62.82) topology. Detailed photophysical behaviors have been explored on Eu3+, Tb3+, and Gd3+ complexes. The calculated triplet state energies of H6L1 and H6L2 lie above the emissive levels of Eu3+ or Tb3+ in an ideal range for sensitizing. Furthermore, it is demonstrated that the optimum energy gap between the triplet state of ligand H6L1 and the emissive level of Tb3+ ion mak...

Two 3D lanthanide frameworks, [Ln7(DPA)5(NA)3(μ3-OH)8(H2O)3]·2.5H2O [H2DPA = diphenic acid; HNA = nicotinic acid; Ln = Gd (1), Dy (2)], were synthesized and structurally characterized. They were rarely seen examples of 3D frameworks constructed from heptanuclear trigonal-antiprismatic lanthanide clusters with mixed H2DPA and HNA ligands. Both 1 and 2 show typical antiferromagnetic interactions. Additionally, complex 1 possesses a large magnetocaloric effect of 34.15 J kg(-1) K(-1).

Self-assembly of Co(II)/Cd(II) with 4,4′-sulfonyldibenzoic acid and bis(4-pyridylmethyl)piperazine has produced 3D interpenetrated and non-interpenetrated polythreading networks with non-trivial linkages.

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.

Two novel coordination polymers [Ca4(C4AS)2(μ3-2,2′-bpno)•15H2O]n•2nH2O (1) and [Cu(H2O)6]n•[Cu2(TC4AS)(μ-2,2′-bpno)•3H2O]n•10nH2O (2) (C4AS=p-sulfonato-calix[4]arene, TC4AS=p-sulfonatothiacalix [4]arene and 2,2′-bpno=2,2′-bipyridine-1,1′-dioxide) have been synthesized and characterized. X-ray diffraction analyses reveal that the rail-like chains of 1 composed of bicapsule units in upper-to-upper way are parallel to the bilayers of 1, whereas the zigzag-like chains of 2 made up of capsules via upper-to-lower mode run through the bilayers of 2. The magnetic properties of complex 2 were examined, indicating weak ferromagnetic interactions between the copper(II) ions in the temperature range of 20–300 K.

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.

Solvothermal reactions of thiacalix[4]arene, NaN3, and acetonitrile in the presence of nickel(II)/cobalt(II) salts yielded four discrete complexes sustained by the in situ generated 5-methyltetrazolate ligand, [NiII12(PTC4A)3(μ6-CO3)2(μ-Mtta)2(μ-Mtta)4 (μ4-Mtta)2(Py)4]·7DMF·2Py·dma (1), [CoII12(PTC4A)3(HCOO)3(μ6-CO3)2 (μ-Mtta)(μ-Mtta)2(μ4-Mtta)2(Py)4]·5DMF·dma (2), [CoII12(BTC4A)3(HCOO)2 (μ6-CO3)2(μ-Mtta)4(μ4-Mtta)2(dma)2(Pz)2]·2DMF·3dma (3), and [CoII16(BTC4A)4(μ4-Cl)4 (HCOO)2(μ-Mtta)6(μ-Mtta)8]·10DMF·6CH3CN·4Hdma (4) (H4PTC4A = p-phenylthiacalix[4]arene; H4BTC4A = p-tert-butylthiacalix[4]arene; HMtta = 5-methyl tetrazolate). Crystal structural analyses revealed that complexes 1–3 are stacked by pseudotrigonal planar entities, which consist of three metalII4-thiacalix[4]arene subunits including two shuttlecock-like and one cylinder-like ones. These subunits are connected in an up-to-down-to-up fashion through six different 5-methyl tetrazolate anions. Both the in situ generated 5-methyl tetrazolate anion...

Four indium(III)-biphenyl carboxylate coordination complexes: [In(dpdc)(bipy)Cl]2 (1), {[In(Hdptc)(bipy)]2·H2O}n (2), [In(dptc)·H3O]n (3), [In3(μ2-OH)2(Hdptc)(dptc)H2O]n (4) (H2dpdc = diphenyl-2,2′-dicarboxylic acid, bipy = 2,2′-bipyridine, H4dptc = biphenyl-2,2′,6,6′-tetracarboxylic acid) have been synthesized under hydrothermal and solvothermal conditions. Complex 1 exhibits a dimeric molecule structure featuring a square motif organized by two In(III) ions and two dpdc ligands each at the corner; 2 contains a similar dimeric segment which is extended into a 1D ribbon structure by the Hdptc ligands and further assembled into 2D supramolecular layer through hydrogen bonding; 3 features a 2D (4,4) grid layer, which is assembled into 3D supramolecular network through hydrogen bonding with guest water molecules. Complex 4 consists of an unprecedented eight-connected trinuclear In3(μ2-O)2(CO2)8 building unit which is jointed by four-connected dptc ligand into a binodal (4,8)-connected scu topology. The results present a feasible way of manipulation to control the dimensionality of the complexes by adjusting ligands and reaction temperatures. The complexes are also characterized by X-ray powder diffractions (PXRD), infrared spectroscopy and elemental analysis.

Reactions of a tripodal ligand, N,N',N″-tris(3-pyridinyl)phosphoric triamide (TPPA), and a series of transition-metal ions result in the assembly of five discrete M(6)L(8) coordination cages [M(6)(TPPA)(8)(H(2)O)(12)](ClO(4))(12)·57H(2)O [M = Ni(2+) (1), Co(2+) (2), Zn(2+) (3), Cd(2+) (4)] and [Pd(6)(TPPA)(8)]Cl(12)·22H(2)O (5). X-ray structural analyses reveal that the cages have large internal cavities and flexible windows. The flexible ligand TPPA adopts the syn conformation in cages 1-4, but it transforms to the anti conformation in cage 5. Because of the conformational transformation, the sizes of the windows and the volume of the internal cavity of cage 5 are increased. (1)H NMR and electrospray mass spectrometric studies show that cage 5 maintains its structural integrity in solution. Additionally, compounds 3 and 4 exhibit strong blue fluorescent emissions, which are 1 order of magnitude higher than that of the free ligand.

Solvothermal reactions of 2,2′-biphenyldicarboxylate (H2dpa) and 4,4′-azobispyridine (azpy) in the presence of transition metal ions produce six new complexes, namely, [Co(dpa)(bphy)]n (1), [Co(dpa)(azpy)(H2O)]n·0.5nH2O (2), [Zn(dpa)(bphy)]n (3), [Zn(dpa)(azpy)(H2O)]n (4), [Mn(dpa)(azpy)(H2O)]n·0.5nH2O (5), and [Mn(dpa)(azpy)]n·nH2O·nMeOH (6) (bphy = 1,2-bis(4-pyridyl)hydrazine). The crystal structure analyses reveal that complexes 1 and 3 are isostructural which features a plywood-like structure, while complex 4 exhibits a parallel chains array. Complexes 2 and 5 afford a two-dimensional chiral (4,4) network, and complex 6 shows a (4,4) network. It was noteworthy that the in situ reduction of azpy to bphy was found in complexes 1 and 3, which were confirmed by single-crystal structures and LC-MS analyses. However, this in situ reduction was not found at a low reaction temperature in the syntheses of complexes 2, 4, and 5. The second-harmonic-generation (SHG) properties of 1 and 3 and the solid circular d...

From our recently reported [Ag2L2]2+ metallacyclic species (L = 2,5-bis(4-pyridinylmethylthio)-1,3,4-thiadiazole), four coordination networks [Ag2L2]n·2n(ClO4)·7nH2O (1), [Ag2L2]n·2n(BF4)·5nH2O (1a), [Ag2L2]n·n[Ag2L2]·4n(NO3) (2) and [AgL(NO2)]n (3) were synthesized under the different anion conditions, which can be classified into three distinct supramolecular structures. Complexes 1/1a are constructed by disilver(I) macrocyclic motifs with the chair conformation, whereas 2 consists of two types of boat-form metallacycles. In 3, the bridging L adopts an extended conformation in sharp contrast to that in 1/1a/2. In this system, conformations of the metallacyclic subunit and flexible ligand L are modulated by various counter anions. For weakly coordinating anions, anion-exchange results indicate that complexes 1/1a maintain the primary structures and have an affinity order in agreement with the Hofmeister series. It is noteworthy that when complexes 1/1a/2 are treated with an aqueous solution containing NO2−, they all undergo a fast and quantitative anion-exchange process to afford complex 3. This process accompanies remarkable conformational conversion of L from cis, cis, syn to trans, trans, syn form. Atomic force microscopy studies indicate a solvent-mediated rather than a solid-state mechanism for the anion exchange.

Treatment of bix (1, 4-bis(imidazole-1-ylmethyl)benzene) with AgI generated [(Ag4I4)(bix)]n 1, 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.

The MnII and CuII compounds of 3-(2-pyridyl)-5,6-diphenyl-1,2,4-triazine-4,4′-disulfonic acid (H2pdtd) were synthesized and systematically characterized. The metal-organic framework (MOF) [Mn2(pdtd)2(H2O)4]n·5nH2O (1) was constructed by a solvothermal method preformed at 140 °C with methanol as the solvent, while [Cu(pdtd)(H2O)4]·H2O (2) was obtained by conventional solution chemistry conducted at 80 °C. Crystallographic analysis revealed that 1 has an acentric structure in which the MnII centers are linked via sulfonate groups and chelating nitrogen atoms within the pdtd ligands to give a rare noninterpenetrating (10,3)-d framework with permanent helical cavities. Consequently, 1 exhibits nonlinear optical (NLO) activity, significant CO2 sorption, and magnetic coupling. In contrast, 2 is a mononuclear complex with coordinated water and lacks functional properties.

Two novel compounds, [Zn(H2PIDC)2(H2O)2] (1) and [Zn4(PIDC)2(SO4)(H2O)5]·(2.5H2O) (2) (H3PIDC = 2-(pyridin-4-yl)-1H-imidazole-4,5-dicarboxylic acid) have been synthesized under hydrothermal condition, and characterized by thermal analyses (TGA), powder X-ray diffractions (PXRD), and single-crystal X-ray diffractions, respectively. Compound 1 is constructed from mononuclear molecules which form the 2D square networks and further extend to 3D supermolecular framework through the π–π stacking and strong hydrogen bonding interactions. Compound 2 exhibits a 3D framework and generates the 1D open rhombic channels filled with the coordinated water molecules, sulfate anions and free water molecules. The structure of 2 can be rationalized as a (4,4,4)-connected net and shown as a unique (4.53.6.7)4(42.52.72)2(52.62.72) topology. The different luminescent nature for 1 and 2 may be due to their various delocalization environments.

Four nickel(II)-5-aminodiacetic isophthalate coordination polymers with different auxiliary ligands are synthesized by the solvothermal method. {[Ni4(adip)2(H2O)10]·6H2O}n (1) (H4adip = 5-aminodiacetic isophthalic acid) is a supermolecular structure assembled by two-dimensional (2D) layers, and it can be viewed as a novel binodal (3,4)-connected topological net with a Schlafli symbol of (4.6.8)4(62.82.102) which has not been reported in the literature. When dipyridyl auxiliary ligands with different spacers are engaged in the reactions to pillar the 2D layers of 1, the 3D frameworks of complexes 2–4 are obtained. {[Ni3(Hadip)2(bpy)2(H2O)4]·9H2O}n (2) (bpy = 4,4′-bipyridine) was crystallographically characterized to be a three-dimensional (3D) coordination network with SPC519 type topology. {[Ni8(adip)4(bpy)(H2O)18]·10H2O}n (3) as a 3D framework exhibits a scarcely reported (3,5)-connected topology with a Schlafli symbol of (4.6.8)4(62.86.102). {[Ni2(adip)(bpp)(H2O)2]·2H2O}n (4) (bpp = 1,3-bis (4-pyridyl)p...

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.

Tripodal host 2,4,6-tris(1-phenyl-1H-tetrazolylsulfanylmethyl)mesitylene (TPTM) has been synthesized through a facile procedure. As expected, it adopts an all-syn cylindrical configuration, thereby delimiting an inner cavity. To explore the solvatomorphism and inclusion behavior of TPTM, a series of organic and inorganic species were employed as guests to afford 17 inclusion compounds (1, 2, 3 a-3 f, 4 a-4 i) that can be classified into four distinct forms (forms I-IV), under similar conditions. These compounds were characterized by single-crystal and powder X-ray diffraction, and (1)H NMR studies. In compound 1 with form I, one foot of a TPTM molecule inserts into the cavity of an opposite TPTM molecule to form a dimeric "hand-shake" motif with one acetonitrile molecule occupying the void. Compound 2 with form II contains three types of capsule-shaped dimers, each of which holds a CH(2)Cl(2) molecule as the guest. In compounds 3 a-3 f with form III, each pair of TPTM molecules interdigitates to form a capsule-shaped dimeric unit accommodating a guest molecule in the endo-cavity. In compounds 4 a-4 i with form IV, each TPTM molecule makes contact with three nearby TPTM molecules in a "self-including" manner to generate a graphite-like organic layer, and through further superposition to form open hexagonal channels. From the experimental and theoretical results, the intrinsic properties of guest molecules, such as size, shape, and self-interaction, can be regarded as the main factors leading to these solvatomorphism phenomena and the subtle inclusion behavior of TPTM. Thermogravimetric analyses show that the encapsulated guest molecules in these compounds can be evacuated at relatively high temperatures, and this demonstrates the outstanding inclusion capability of TPTM. In addition, for compound 4 a with benzene molecules in the channels, reversible exchange of toluene and separation of xylene isomers on single crystals have been observed.

Five Mn II -sdba coordination polymers with mono-, di-, tri-, tetra-nuclear cores based on the V-shaped 4,4′-dicarboxybiphenyl sulfone (H 2 sdba) ligands: [Mn(sdba)(phen) 2 (H 2 O)] n ·3 n H 2 O ( 1 ), [Mn 2 (sdba) 2 (μ-H 2 O)(py) 4 ] n ( 2 ), [Mn 3 (sdba) 2 (Hsdba) 2 (2,2′-bipy) 2 ] n ( 3 ), [Mn 4 (sdba) 4 (4-mepy) 2 (H 2 O) 4 ] n ·2 n H 2 O ( 4 ) and [Mn 4 (sdba) 4 (bpp) 4 (μ-H 2 O) 2 ] n ·0.5 n H 2 O ( 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 Mn 4 units. The magnetic susceptibility studies in the 2–300 K range for these complexes reveal the existence of anti-ferromagnetic exchange interactions between the Mn II ions.

[Co3(1,2-S2C6H4)3(PPh3)3][CoBr3(DMF)]sol (1, sol=CHCl3·O(C2H5)2·H2O) was obtained from the reaction of CoBr(PPh3)3 with Na2(S2C6H4) in chloroform. The Co3 core in the cation of 1 exhibits a metal-metal bonded isosceles triangle, in which the two longer Co—Co bonds are both bridged by S2C6H4 ligands on two sides of the triangle plane respectively, while the bottom short Co—Co bond is bridged by the third bidentate S2C6H4 ligand. A series of polynuclear cobalt cluster compounds with phosphine, thiolate and/or sulphur ligands were prepared by low oxidation state Co+ with thiolates in organic solvents. These tri-, tetra-, hexa-, heptanuclear cluster compounds 1–8 with various types of crystal structures can be viewed as the condensed polynuclear cobalt complexes that the cobalt atom frameworks with sulphur bridged were built through the small triangular units of [Co3S3nL3] (n=1,2) with or without [CoL] (L=PR3, Br, Cl,5-C5H5) fragments.

[V2(μ-S2)2(S2CNEt2)4] 2CH3Cl was synthesized by the reaction of NaS2CNEt2, Li2S and VOCl3 at room temperature. Crystal data: M= 1061.3, space group Pbca, with the orthorhombic parameters: a=20.123(3), b = 20.485(4)1c=10.911(3)A, V=4497.7A3, Z=4, Dc=1.57 g/cm3, Mo Ko radiation (λ=0.71069 A), μ = 13.2 cm−1, F(000)—2168. Final R = 0.041 and Rw=0.047 for 2288 observed reflections with I>3σ(I). The coordination sphere of each V atom in title compound is a distorted tetragonal prism composed of two bidentate dithiocarbamate and two S21− ligands. The V—V distance is 2.890 A while the V—S distances fall in the range of 2.422–2.505 A.

Co4(μ3-S)8(Ph2PCH2sP(O)Ph2)6, MW = 3012.5, space group R3, has the hexagonal parameters, a = 26.764 (10), c = 16.979 (10) A, V = 10532.8 A3, Z = 3. Mo Ka radiation, λ = 0.71069 A, Dc = 1.425 g/cm3, μ = 9.94 cm−3, F(000) = 4650, R = 0.073 and Rw = 0.077 for 1965 observed unique reflections with I > 3σ (I). The molecular structure consists of a distorted octahedral Co4—core. The Co—Co and Co—S distances fall in the range of 2.805—2.838 and 2.213—2.253 A, respectively.

Two isomeric Au complexes, [Au(Stt)Cl]n (1) and [Au(Stt)Cl]4n (2) (Stt = S-trithiane), have been prepared and structurally and spectroscopically characterized. Each compound crystallizes as a unique form with aurophilic interactions between the linear and two-coordinated Au(I) cations. In complex 1, the Au(Stt)Cl molecules self-associate to form 1D nearly linear chains via equivalent aurophilic interactions, whereas the structure of complex 2 features 1D flexural chains composed of zigzag [Au(Stt)Cl]4 tetramers through varying aurophilic interactions. Emission spectra of both complexes at room temperature give strong red luminescence.

A novel red luminescent coordination polymer, [Cu2I2(bmt)]n·nDMF (1), was synthesized from the solution reaction of CuI and heterocyclic thione ligand, benz-1,3-imidazole-2-thione (bmt). Single-crystal analysis shows that its unusual organic–inorganic hybrid framework built-up from the distorted double-stranded zigzag [Cu4I4]n chains with organic bmt ligands. Emission properties of 1 in solid state at room temperature and 10 K were investigated.

A novel In(III) coordination complex, [In(ptc)(H2O)]n (H3ptc = 4,4′,4″-phosphoryltribenzoic acid) (1), was synthesized under hydrothermal condition and characterized by single-crystal X-ray analysis, IR, X-ray powder diffraction (XRD), thermogravimetric analysis (TGA) and solid-state photoluminescence. Complex 1 crystallizes in a chiral P21 space group, In(III) ions are eight-coordinated and the ligand exhibits a novel and unique tetrahedral coordination mode. The complex shows intense blue emission at 435 nm with the excitation of 330 nm.

Assembly of 5-sulfosalicylic acid (H{sub 3}L) and d{sup 10} transition metal ions (Cd{sup II}, Ag{sup I}) with the neutral N-donor ligands produces five new complexes: [Cd{sub 2}(HL){sub 2}(4,4'-bipy){sub 3}]{sub n}.2nH{sub 2}O (1), {l_brace}[Cd{sub 2}(mu{sub 2}-HCO{sub 2}){sub 2}(4,4'-bipy){sub 2}(H{sub 2}O){sub 4}][Cd(HL){sub 2}(4,4'-bipy)(H{sub 2}O){sub 2}]{r_brace}{sub n} (2), {l_brace}[Cd(4,4'-bipy)(H{sub 2}O){sub 4}][HL].H{sub 2}O{r_brace}{sub n} (3), [Cd(HL)(dpp){sub 2}(H{sub 2}O)]{sub n}.4nH{sub 2}O (4), {l_brace}[Ag(4,4'-bipy)][Hhbs]{r_brace}{sub n} (5) (4,4'-bipy=4,4'-bipyridine, dpp=1,3-di(pyridin-4-yl)propane, H{sub 2}hbs=4-hydroxybenzenesulfonic acid, the decarboxylation product of H{sub 3}L). Complex 1 adopts a 5-connected 3D bilayer topology. Complex 2 has the herring-bone and ladder chain, which are extended to a 3D network via hydrogen bonding. In 3-4 complexes, 3 is a 3D supermolecular structure formed by polymeric chains and 2D network of HL{sup 2-}, while 4 gives the double-stranded chains. In 5, ladder arrays are stacked with the 2D networks of Hhbs{sup -} anions in an -ABAB- sequence. Complexes 1-4 display green luminescences in solid state at room temperature, while emission spectra of 3 and 4 show obvious blue-shifts at low temperature. - Graphical abstract: Reactions of 5-sulfosalicylic acid (H{sub 3}L) and d{sup 10} metal ions (Cd{sup II}, Ag{sup I}) produce five new complexes. Complexes 1-4 all display green luminescences at room temperature.

Reactions of 2,2′-dihydroxyl-[1,1′]-binaphthalene-3,3′-dicarboxylate acid (H2bna) with manganese chloride by a solvent or solvothermal method in the presence of pyridine (py) or 4-picoline (pic) give birth to three 1D to 3D frameworks: [Mn(bna)(DMF)2(H2O)2]n·nDMF (1), {(Hpic)2[Mn3(bna)4(C2H5OH)2(H2O)2]·5H2O}n (2), and {(Hpy)2[Mn3(bna)4(py)2(H2O)2]·4H2O}n (3) (DMF = N,N′-dimethylformamide). Crystal structure analyses reveal that 1 is a mesomer with equivalent R- and L-helical rectangular tubes constructed from homochiral ligands, which is further assembled into a 3D supramolecular network through hydrogen bonds and C−H···π interactions. Complex 2 consists of a (4,4) grid chiral layer structure, while 3 features a 3D cubic diamond network with Schlafli symbol 66 topology, though they both comprise of [Mn3(μ2-COO)6(COO)2] pinwheel molecular building blocks which act as 4-connected nodes and bna2− as linkers. Magnetic studies indicate that antiferromagnetic couplings exist in both 2 and 3.

Two coordination compounds based on p-sulfonatothiacalix[4]arene (TCAS) were synthesized by hydrothermal reactions of TCAS with M2+ cations (M = Cu for 1, M = Co for 2) in the presence of [PhCH2N(CH3)3]+. Single-crystal X-ray analyses revealed that both compounds, 1 and 2, are isomorphous and crystallize in the same space group . The tetranuclear cluster units are connected into layer networks through complicated hydrogen-bonding and π–π interactions. The results of thermogravimetric measurements demonstrate that 1 and 2 have the high thermal stabilities.