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With the idea of supramolecular hosts encircling monoanions, a series of urea-containing trinuclear cationic copper complexes were designed, prepared and structurally analyzed. Copper(I) acetylides [Cu3(μ-dppm)3(μ3-η1-CCC6H4-4-NHC(O)NHC6H4-4-R)2]+ (dppm = bis(diphenylphosphino)methane; R = NO2 (1), CF3 (2), Cl (3), H (4), tBu (5), and OCH3 (6)) were prepared with F−, BF4−, or NO3− present as the anion. Eight 1-D anion coordination polymers (ACPs), 1·F, 2·F, 3·BF4, 4·F, 5·F, 5·BF4, 5·NO3 and 6·0.5F·0.5BF4, were clearly determined by X-ray diffraction. Diversity in the polymeric architecture is generated by both the choice of R-group used and anion present. 2·F, 3·BF4, 4·F, and 5·F show linear 1-D structures; 5·BF4 and 5·NO3 feature single-stranded helical structures; 1·F and 6·0.5F·0.5BF4 exhibit meso-helical structures. Solid state UV-vis absorption and luminescence properties are also discussed.

A series of gold(I) acetylide complexes, Cy3PAuC CC6H4-C(O)R-4 (R H (1), Me (2), OMe (3), NH2 (4)) (Cy3P = tricyclohexylphosphine), have been synthesized and characterized. The crystal structures of Cy3PAuC CC6H4-C(O)H-4 (1) and Cy3PAuC CC6H4-C(O)NH2-4 (4) were determined by X-ray diffraction. The photophysical properties of complexes 1–4 have been studied. Complexes 1–4 show luminescence both in the solid state and in acetonitrile solution at 298 K, and their emission energies are in the order: 4 > 3 > 2 > 1.

Two new oxalate-bridged Gd(III) coordination polymers, namely, (choline)[Gd(C2O4)(H2O)3Cl]Cl·H2O (1) and [Gd(C2O4)(H2O)3Cl] (2), were first obtained ionothermally by using a deep eutectic solvent (DES). The magnetic studies and heat capacity measurements reveal that the two-dimensional Gd(III)-based coordination polymer of 2 has the higher magnetic density and exhibits a larger cryogenic magnetocaloric effect (MCE) (ΔS(m) = 48 J kg(-1) K(-1) for ΔH = 7 T at 2.2 K).

A series of mononuclear gold(I) acetylide complexes with amide groups, Ph3PAuCCC6H4NHC(O)C6H4–R-4 (R = NO2 (3a), CF3 (3b), H (3c), and OMe (3d)), has been synthesized and characterized. The crystal structure of Ph3PAuCCC6H4NHC(O)C6H4–NO2-4 (3a) was determined by X-ray diffraction. The photophysical properties of gold(I) acetylide complexes 3b–3d were studied and the complexes show luminescence both in the solid state and in degassed THF solutions at 298 K. The anion-binding abilities of complexes 3a–3d in CDCl3 were also studied through 1H NMR titration experiments. They show similar anion selectivity trends and 3a exhibits the highest binding affinity towards anions due to the strongest electron-withdrawing ability of the NO2 group. In DMSO, 3a shows a dramatic color change upon addition of F−, which provides access to naked eye detection of F−.

A series of mononuclear gold(I) acetylide complexes with urea moiety, R'(3)PAuC≡CC(6)H(4)-4-NHC(O)NHC(6)H(4)-4-R (R' = cyclohexyl, R = NO(2) (2a), CF(3) (2b), Cl (2c), H (2d), CH(3) (2e), (t)Bu (2f), OCH(3) (2g); R' = phenyl, R = NO(2) (3a), OCH(3) (3b); R' = 4-methoxyphenyl, R = H (4a), OCH(3) (4b)), have been synthesized and characterized. The crystal structures of Ph(3)PAuC≡CC(6)H(4)-4-NHC(O)NHC(6)H(4)-4-NO(2) (3a) and (4-CH(3)OC(6)H(4))(3)PAuC≡CC(6)H(4)-4-NHC(O)NHC(6)H(5) (4a) have been determined by X-ray diffraction. Complexes 2a-2g, 3b, and 4a-4b show intense luminescence both in the solid state and in degassed THF solution at 298 K. Anion binding properties of complexes 2a-2g, 3a-3b, and 4a-4b have been studied by UV-vis and (1)H NMR titration experiments. In general, the log K values of 2a-2g with the same anion in THF depend on the substituent R on the acetylide ligand of 2a-2g: R = NO(2) (2a)CF(3) (2b) ≥ Cl (2c)H (2d)CH(3) (2e) ≈ (t)Bu (2f) ≥ OCH(3) (2g). Complex 2a with NO(2) group shows the dramatic color change toward F(-) in DMSO, which provides an access of naked eye detection of F(-).

The axially chiral conformations of 2,2′-bipyridine are, for the first time, captured and isolated in individual crystals of a new family of three-dimensional coordination polymers [Mn(II)(2,2′-bpy)(HCO2)2–x(N3)x] (x = 0.3–0.7) upon an unusual spontaneous resolution. Furthermore, the Mn(II)···Mn(II) magnetic exchange can be tuned by control of the ratio of N3–/HCO2–.

This review gives an overview on the coordination chemistry of eight cyclohexanepolycarboxylic acids, i.e. cyclohexanecarboxylic acid, 1,2-, 1,3- and 1,4-cyclohexanedicarboxylic acid, 1,3,5- and 1,2,4-cyclohexanetricarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid and 1,2,3,4,5,6-cyclohexanehexacarboxylic acid, and explores their possible applications in materials science, especially as magnetic materials. The conformational transformation of cyclohexanepolycarboxylic acids in the presence of various metal ions under hydrothermal conditions is included and the α-proton removal mechanism is discussed as well.

Two enantiomeric Schiff base ligands R-/S-H2L in situ generated from the condensation of o-vanillin with R- or S-2-phenylglycinol were applied to assemble chiral multinuclear transition metal magnetic clusters for the first time. Four new enantiomerically pure chiral clusters, [NaMn4(3-O)(N3)1.75Br0.25(R-L)3(MeOH)2(H2O)2][NaMn4(mu3-O)(N3)2(R-L)3(MeOH)2(H2O)2]Br4 (1R), [NaMn4(mu3-O)(N3)1.75Br0.25(S-L)3(MeOH)2(H2O)2][NaMn4(mu3-O)(N3)2(S-L)3(MeOH)2(H2O)2]Br4 (1S), [Cu6(R-L)2(R-HL)2(N3)5(MeOH)]NO3.2MeOH.H2O (2R) and [Cu6(S-L)2(S-HL)2(N3)5(MeOH)]NO3.2MeOH.H2O (2S), have been synthesized and characterized by single crystal X-ray crystallography and CD spectroscopy. Three Mn(III) in the MnIIMnIII3 clusters of 1R and 1S are joined together through the 3-O bridge to form an oxo-centered Mn3O unit. Three L2- link four manganese atoms via the mu2-O,N,O-bridging manner into a MnIIMnIII3 cluster in a distorted tetrahedral geometry. Enantiomeric 2S and 2R are hexanuclear copper(II) clusters composed of a cubane-like Cu4L4 part with a dinuclear Cu2(N3)2 unit capped on one of the faces of the Cu4L4 cubane via the mu1,1-azide and phenolate bridges from the chiral ligands. Magnetic analysis reveals intracluster antiferromagnetic interaction between adjacent manganese ions in chiral oxo-centered MnIIMnIII3 magnetic clusters for 1R and 1S, and dominating antiferromagnetic over weak ferromagnetic interactions in Cu6 clusters in 2R and 2S.

Hydrothermal reactions of 2,3,5-trimethylpyridine (2,3,5-tmpy) yielded two pyridinecarboxylates, 3,5-dimethyl-2-pyridinecarboxylate (2-dmpya) and 3-methyl-2,5-pyridine dicarboxylate (2,5-mpyda) in the presence of copper nitrate. The in situ generated pyridinecarboxylates were derived from copper-mediated stepwise oxidation of 2- or/and 5-methyl groups on the pyridine by nitrate in acidic aqueous solution. The selectivity might be due to the different electronic distribution resulting from the asymmetric substitution on the aromatic ring and steric hindrance between two neighboring methyl groups. When 2,4,6-trimethylpyridine (2,4,6-tmpy) was used in the reactions, the three evenly-distributed methyl groups were oxidized simultaneously to form 2,4,6-pyridine tricarboxylate (2,4,6-pyta). Interestingly in nearly neutral solution a new ligand 3-hydroxy-2,4,6-pyridine tricarboxylate (2,4,6-Opyta) was yielded and trapped in the compound [Cu4(2,4,6-Opyta)2(H2O)6]·2H2O (4). The in situ copper-mediated oxidation of 2,4,6-tmpy to 2,4,6-Opyta4−via 2,4,6-pyta3− can be further supported by the formation of 4 from a hydrothermal reaction of 2,4,6-pyridine tricarboxylic acid with copper nitrate at 185 °C for 4 days. The new Opyta ligand was isolated as an ammonium (NH4)(2,4,6-OpytaH3)·H2O and characterized by NMR, MS and X-ray crystallography. The magnetic property of 4 was investigated.

The hydrothermal synthesis and crystal structures of four coordination polymers, namely, 2D [Zn(μ3-ta)(pytaH)] n (1), 2D [Zn(μ3-pyta)Cl] n (2), 1D [Cd(μ-pyta)2(H2O)] n (3), and 3D [Cd(μ3-pyta)(μ-Cl)] n (4) (pyta = (4-pyridylthio)acetate, ta = thioglycolate), are reported. They are based on (4-pyridylthio)acetate and its derived ligand. The ta2− ligand present in 1 was generated from an in situ C(sp2)-S bond cleavage of the pyta ligand. In these compounds, versatile intermolecular interactions, such as close S…S interactions and strong (O-H…O/N/S) or weak (C-H…O/S, C-H…Cl) hydrogen bonding interactions, play an important role in the formation of three-dimensional supramolecular networks in the solid state.

Hydrothermal reactions of CdCl2, oxalic acid, 1,3,5-benzenetricarboxylic acid and o-phenylene diamine (o-PD) yielded three novel coordination polymers [NaCd4(btc)3(H2bbim)4(H2O)2]·2H2 O( 1), [KCd4(btc)3(H2bbim)4(H2O)2]·2H2 O( 2) and [Cd(H2bbim)(H2bimbdc)(HbimbdcH)]·H2 O( 3) [btc = 1,3,5benzene tricarboxylate, H2bbim = 2,2-bisbenzimidazole, HbimbdcH2 = 1-(2-Benzimidazolyl)-3,5-benzene dicarboxylic acid]. The benzimidazole derivatives were in situ gener

To study the conformations and coordination chemistry of cyclohexane-1,2,4,5-tetracarboxylic acid (H4L), we have obtained four new coordination polymers, [Mn2(μ4-LI)(H2O)6] (1), [Mn2(μ8-LI)(H2O)2] (2), [Mn2(μ7-LII)(H2O)3] (3), and [Ag4(LI)(4,4′-bpy)3]·10H2O (4), from the reactions of Mn(II) or Ag(I) salts with cyclohexane-1e,2a,4a,5e-tetracarboxylic acid (2e+2a, H4LI). A new conformation, cyclohexane-1e,2a,4e,5e-tetracarboxylate (3e+1a, LII), was derived from conformational conversions of LI and trapped in 3 upon coordination by controlling the hydrothermal reaction conditions. The stabilization and separation of different conformations of the flexible organic ligands in coordination structures may help us understand and utilize various interesting conformational transformations. Magnetic studies show that antiferromagnetic interaction occurs in both 1 and 2.

To study the conformations of 1,2,3,4,5,6-cyclohexanehexacarboxylic acid (H(6)L), eleven new coordination polymers have been isolated from hydrothermal reactions of different metal salts with 1e,2a,3e,4a,5e,6a-cyclohexanehexacarboxylic acid (3e+3a, H(6)L(I)) and characterized. They are [Cd(12)(mu(6)-L(II))(mu(10)-L(II))(3)(mu-H(2)O)(6)(H(2)O)(6)]16.5 H(2)O (1), Na(12)[Cd(6)(mu(6)-L(II))(mu(6)-L(III))(3)]27 H(2)O (2), [Cd(3)(mu(13)-L(II))(mu-H(2)O)] (3), [Cd(3)(mu(6)-L(III))(2,2'-bpy)(3)(H(2)O)(3)]2 H(2)O (4), [Cd(4)(mu(4)-L(VI))(2)(4,4'-Hbpy)(4)(4,4'-bpy)(2)(H(2)O)(4)]9.5 H(2)O (5), [Cd(2)(mu(6)-L(II))(4,4'-Hbpy)(2)(H(2)O)(10)]5 H(2)O (6), [Cd(3)(mu(11)-L(VI))(H(2)O)(3)] (7), [M(3)(mu(9)-L(II))(H(2)O)(6)] (M=Mn (8), Fe (9), and Ni (10)), and [Ni(4)(OH)(2)(mu(10)-L(II))(4,4'-bpy)(H(2)O)(4)]6 H(2)O (11). Three new conformations of 1,2,3,4,5,6-cyclohexanehexacarboxylate, 6e (L(II)), 4e+2a (L(III)) and 5e+1a (L(VI)), have been derived from the conformational conversions of L(I) and trapped in these complexes by controlling the conditions of the hydrothermal systems. Complexes 1 and 2 have three-dimensional (3D) coordination frameworks with nanoscale cages and are obtained at relatively low temperatures. A quarter of the L(I) ligands undergo a conformational transformation into L(II) while the others are transformed into L(III) in the presence of NaOH in 2, while all of the L(I) are transformed into L(II) in the absence of NaOH in 1. Complex 3 has a 3D condensed coordination framework, which was obtained under similar reaction conditions as 1, but at a higher temperature. The addition of 2,2'-bipyridine (2,2'-bpy) or 4,4'-bipyridine (4,4'-bpy) to the hydrothermal system as an auxiliary ligand also induces the conformational transformation of H(6)L(I). A new L(VI) conformation has been trapped in complexes 4-7 under different conditions. Complex 4 has a 3D microporous supramolecular network constructed from a 2D L(III)-bridged coordination layer structure by pi-pi interactions between the chelating 2,2'-bpy ligands. Complexes 5-7 have different frameworks with L(II)/L(VI) conformations, which were prepared by using different amounts of 4,4'-bpy under similar synthetic conditions. Both 5 and 7 are 3D coordination frameworks involving the L(VI) ligands, while 6 has a 3D microporous supramolecular network constructed from a 2D L(II)-bridged coordination layer structure by interlayer N(4,4'-Hbpy)--HO(L(II)) hydrogen bonds. 3D coordination frameworks 8-11 have been obtained from the H(6)L(I) ligand and the paramagnetic metal ions Mn(II), Fe(II), and Ni(II), and their magnetic properties have been studied. Of particular interest to us is that two copper coordination polymers of the formulae [{Cu(II) (2)(mu(4)-L(II))(H(2)O)(4)}{Cu(I) (2)(4,4'-bpy)(2)}] (12 alpha) and [Cu(II)(Hbtc)(4,4'-bpy)(H(2)O)]3 H(2)O (H(3)btc=1,3,5-benzenetricarboxylic acid) (12 beta) resulted from the same one-pot hydrothermal reaction of Cu(NO(3))(2), H(6)L(I), 4,4'-bpy, and NaOH. The Hbtc(2-) ligand in 12 beta was formed by the in situ decarboxylation of H(6)L(I). The observed decarboxylation of the H(6)L(I) ligand to H(3)btc may serve as a helpful indicator in studying the conformational transformation mechanism between H(6)L(I) and L(II-VI). Trapping various conformations in metal-organic structures may be helpful for the stabilization and separation of various conformations of the H(6)L ligand.

The first coordination compounds of partially or wholly deprotonated benzenepentacarboxylic acid (H5L) were synthesized in the presence or absence of auxiliary 2,2'-bipyridyl (2,2'-bpy) and 1,10-phenanthroline (phen) ligands, and their crystal structures and photoluminescent properties were characterized. Their formulas are [Zn6(mu3-OH)2(L)2(H2O)6]n (1), [Zn5(mu3-OH)2(HL)2(2,2'-bpy)2]n (2), [Zn2(HL)(phen)2(H2O)2]n (3), and [Zn5(L)2(phen)4(H2O)3]n.2nH2O (4). Both 1 and 2 are three-dimensional (3D) zinc(II)-hydroxide cluster based coordination frameworks. 1 contains distorted chairlike hexanuclear Zn6(mu3-OH)2 cluster units as secondary building blocks. Each Zn6(mu3-OH)2 unit connects six others through the three-connected nodes of L5- ligands into a 3D rigid and condensed coordination network, whereas in 2, each pentanuclear Zn5(mu3-OH)2 unit connects the other six ones through the three-connected [HL]4- nodes into a 3D network in the simple cubic packing mode. 3 has two-dimensional (2D) Zn(II)-carboxylate supramolecular layers constructed from a one-dimensional (1D) coordination chain structure by hydrogen bonds of the water and mu5-[HL]4- bridges, whereas 4 has 2D coordination layers composed of Zn(II) and mu8-L5- bridges. The adjacent coordination assemblies in 3 and 4 are further extended by hydrogen bonds and pi...pi interactions into 3D supramolecular architectures. 1-4 are photoluminescent active materials, and their photofluorescent properties are closely related to their intrinsic structure arrangements.

Five new pyridinethiolate-bridged 2D and 3D coordination networks of d10 metal halides formulated with [Cu2(SCN)(4-pyt)] (1), [Ag2Cl2(4-pytH)] (2), [Cu5(SCN)3(2-pyt)2] (3), [Cu4I4(2-pytH)] (4), and [Ag3Cl3(2-pytH)2] (5) (4-pyt = 4-pyridinethiolate, 2-pyt = 2-pyridinethiolate) have been solvothermally synthesized, in which the pyt or pytH ligands were generated via in situ cleavage of S–S bonds of 4,4′-dithiodipyridine (4-dtdp) or 2,2′-dithiodipyridine (2-dtdp) in the presence of Cu(I) or Ag(I) ions. Complexes 1 and 3 are a 3D coordination network, constructed with the interesting inorganic Cu–S coordination layers in a (6,3) topology net bridged by the 4-pyt and SCN ligands for 1 and constructed with the (CuSCN)n layers linked by the 2-pyt-supported (Cu6S6) units for 3. Complexes 2, 4, and 5 are 2D coordination layer structures, which are constructed with 1D (AgCl)n ladder chains linked by [Ag2(4-pytH)2] bridges for 2, with double step-ladder and zigzag (CuI)n chains linked by μ3-2-pytH bridges for 4, and...

Three solid compounds formulated as [Cu(ClpyOH)4(H 2 O) 2 ](PF 6 ) 2 .(ClpyOH)4 1, [Co(pyOH) 4 (H 2 O) 2 ](ClO 4 ) 2 2, and [Fe(ClpyoH) 4 Br 2 ] 3 (ClpyOH = 5-chloro-2-hydroxy pyridine; pyOH = 2-hydroxy pyridine) have been shown by single-crystal structural analysis to be 3D networks, which are constructed by metal cation-supported crown ether-like species featuring hydrogen-bonded tetrameric unit of 2-hydroxy pyridines through extensive intermolecular interactions. The similar 16-membered hydrogen-bonded macrocyclic rings are still remaining in their solid structures when the molar ratio of M(II) and ligand were changed to 1:2 or 1:3 in their reaction systems for 1-3, suggesting that this kind of macrocyclic ring is more stable than other products of M(II) and ligand. Differences in the overall structural architectures in 1-3 are due to the interplay between the strong O-H...O hydrogen-bonding interactions and/or a variety of weaker interactions involving the halogens, C-H donors, and the aromatic systems.

Two new isostructural coordination polymers with novel anionic metal-organic frameworks are synthesized under microwave conditions using an ionic liquid EMIm-Br as solvent and template.

Two novel isostructural oxalate-bridged lanthanide(III) chains, (choline)[Ln(ox)(H2O)3Cl]Cl·H2O (Ln = Dy/Er), were first obtained ionothermally by using a choline chloride–oxalic acid eutectic mixture as both solvent and structure-directing agent, both of which show field-induced slow relaxation of magnetization.

A general approach was developed to synthesize a series of cobalt, manganese, and iron phosphate frameworks in deep-eutectic solvents through tuning important reaction parameters including temperature, time, and addition of water.

A family of linear Dy3 and Tb3 clusters have been facilely synthesized from the reactions of DyCl3, the polydentate 3-methyloxysalicylaldoxime (MeOsaloxH2) ligand with auxiliary monoanionic ligands, such as trichloroacetate, NO3−, OH−, and Cl−. Complexes 1–5 contain a nearly linear Ln3 core, with similar Ln⋅⋅⋅Ln distances (3.6901(4)–3.7304(3) Å for the Dy3 species, and 3.7273(3)–3.7485(5) Å for the Tb3 species) and Ln⋅⋅⋅Ln⋅⋅⋅Ln angles of 157.036(8)–159.026(15)° for the Dy3 species and 157.156(8)–160.926(15)° for the Tb3 species. All three Ln centers are bridged by the two doubly-deprotonated [MeOsalox]2− ligands and two of the four [MeOsaloxH]− ligands through the N,O-η2-oximato groups and the phenoxo oxygen atoms (Dy-O-Dy angles=102.28(16)–106.85(13)°; Tb-O-Tb angles=102.00(11)–106.62(11)°). The remaining two [MeOsaloxH]− ligands each chelate an outer LnIII center through their phenoxo oxygen and oxime nitrogen atoms. Magnetic studies reveal that both Dy3 and Tb3 clusters exhibit significant ferromagnetic interactions and that the Dy3 species behave as single-molecule magnets, expanding upon the recent reports of the pure 4f type SMMs. ispartof: Chemistry - a European Journal vol:17 issue:8 pages:2458-2466 ispartof: location:Germany status: published

Solvothermal reactions of 1,10-phenanthroline-2,9-dicarbaldehyde dioxime (H(2)phendox) with FeCl(3)·6H(2)O or FeBr(3) under solvothermal conditions yielded two trinuclear iron(III) clusters [Fe(III)(3)(mu(3)-O)(phendox)(3)]X·14H(2)O (X = Cl 1·14H(2)O, Br 2·14H(2)O) and three hexanuclear iron(III) and iron(II) clusters, [Fe(III)(6)(mu(4)-O)(2)(MeO)(6)X(4)(phendox)(2)]·MeOH (X = Cl , Br 4) and (H(3)O)[Fe(II)(6)(mu(6)-Cl)(phenda)(6)]·6H(2)O (5·6H(2)O). The phendox(2-) ligand is very useful in constructing magnetically active and stable high-nuclearity metal clusters in that the phenanthroline rings and the oxime nitrogen atoms grasp the metal ions tightly while the two oxygen atoms on the oximates can link other metal centres in the shortest pairwise magnetic exchange pathway. Adjacent Fe(3)(mu(3)-O)(phendox)(3)(+) motifs in 1 and 2 are packed by off-set pi-pi interactions of the aromatic rings on phendox(2-) to generate a 3D supramolecular architecture in the honeycomb topology and with 1D hexagonal channels in the dimension of 13 x 13 Å along the c-axis. 2 is stable upon the removal of guest molecules and the desolvated compound absorbed considerable amount of N(2), CO(2) and H(2). 3 and 4 are isostructural. Two mu(4)-O(2-) and two phendox(2-) units link four metal atoms into a coplanar butterfly-shaped unit with the mu(4)-O(2-) slightly above and below the plane (+/-0.264 Å). The other two Fe(III) ions are capped on the alternate planes via the three bridging mu(2)-methoxides and accordingly form an unprecedented hexanuclear Fe(III) cluster. Furthermore, the oximes underwent hydrolysis to yield carboxylate groups and the resulted 1,10-phenanthroline-2,9-dicarboxylate link the iron atoms to form a hexanuclear cluster of 5. Magnetic studies show that the antiferromagnetic interactions are present in the Fe(3)O core of 2 and in the (mu(6)-Cl)Fe(6)(mu-O)(12) core of 5.

The first metal phosphate analogue of the zeolite Na-J (framework type JBW) has been synthesized by an ionothermal approach along with zincophosphate thomsonite.

Three microporous Ln-Co-pyta heterometallic compounds [Ln4Co3(pyta)6(H2O)9]·5H2O (Ln = Sm (1), Eu (2), Gd (3); H3pyta = 2,4,6-pyridinetricarboxylic acid) have interesting selective adsorption abilities towards H2/N2 and CO2/N2 because of size-selective effects; magnetic analysis reveals that 3 has a ferromagnetic behavior.

Four new cobalt coordination polymers, (EMIm)[Co2(TMA-H)2(44bpy)3]Br 1, (EMIm)[Co(TMA-H)(44bpy)2](44bpy)Br 2, (EMIm)[Co(TMA)(Im-H)]3 and (EMIm)2[Co(TMA)2(TED-H2)] 4, were prepared from 1-ethyl-3-methyl imidazolium bromide (EMIm-Br). All the compounds have similar two-dimensional cobalt trimesate (TMA) coordination layers but different three-dimensional supramolecular architectures that contain one of three potentially ditopic amines, 4,4'-bipyridine (44bpy), imidazole (Im-H) and triethylenediamine (TED). Two-fold interpenetration of hydrogen-bonding networks was found for 1, 2 and 4. The coordination layers of 1 and 2 are neutral while 3 and 4 have anionic molecular assemblies. The use of organic amines, that act as supramolecular bridging ligands, introduces hydrogen-bond-directing effects in the ionothermal synthesis of metal coordination polymers. Hydrogen bonding helps to align the packing between the coordination layers and control the formation of 3D supramolecular networks. In 1, hydrogen bonds between the ionic species within the channels direct the alignment of non-directional electrostatic interactions between EMIm+ and Br(-) ions, which is a rare case of a hydrogen-bond-templating effect of ionic liquids in ionothermal synthesis.

A new chiral coordination polymer, (BMIm)2[Ni(TMA-H)2(H2O)2], was prepared ionothermally from chiral ionic liquid. The use of l-aspartate as one component of the ionic liquid induces chirality in the resulting solid, despite the fact that the anion is not occluded by the material and that the solid itself is built from only nonchiral building blocks. Without the chiral component, an achiral compound is formed under the same synthesis conditions.

Two anionic 3D coordination frameworks (EMIm)2[Co3(TMA)2(OAc)2] 1 and (EMIm)[Co(TMA)] 2, one condensed hydroxide network [Co5(OH)2(OAc)8](H2O)x 3, and one 2D layer compound (EMIm)[Co2(TMA)4H7(22bpy)2] 4 were prepared from three relevant ionic liquids of 1-ethyl 3-methyl imidazolium bromide (EMIm-Br), EMIm bistriflamide (EMIm-Tf2N), and mixtures of the two. The use of anions in ionic liquids plays a significant role in solvent polarity/hydrophibicity, which in turn controls the structures of materials formed in the ionothermal synthesis. The use of mixed anion ionic liquids opens up many possibilities to further tailor the properties of ionic liquids for ionothermal synthesis applications. The ionic liquid anions are not incorporated into the resultant materials.

Two unique dysprosium(III) coordination compounds with similar dodecanuclear clusters composed of four vertex-sharing cubane-like units, [2Cl− ⊂ {Dy12(OH)16(phenda)8(H2O)8}]2+, were reported. Magnetic studies reveal that both compounds exhibit slow magnetic relaxation.

Four new cobalt coordination polymers based on cyclohexane-1e,2a,4a,5e-tetracarboxylic acid (2e+2a, H4LI), [Co4(μ4-LI)2(4,4′-bpy)3(H2O)6]·2H2O (1), [Co4(μ5-LI)2(4,4′-bpy)3(H2O)4]·3H2O (2), [Co2(μ4-LIV)(2,2′-bpy)2(H2O)2] (3) and [Co2(μ4-LIV)(1,10-phen)2(H2O)2]·4H2O (4), were synthesized in hydrothermal reactions with some auxiliary ligands to study the conformations and coordination chemistry of H4L. The structural analysis revealed a new conformation, cyclohexane-1e,2e,4e,5e-tetracarboxylic acid (4e, H4LIV), for the flexible ligand H4L trapped in compounds 3 and 4, which were synthesized in the presence of different chelating ligands whereas in the compounds of 1 and 2, the ligands adapt the same conformation (2e+2a, H4LI) as found in the solid state when the linear bridging 4,4′-bpy was added as auxiliary ligand. The conformational transformation originated from the removal of α-protons of H4L, which has been confirmed via the production of [CuI(4,4′-bpy)(H2O)]2(ip)·2H2O (5) (H2ip = isophthalic acid) from the reaction of Cu2+ ions, H4LI ligand and 4,4′-bpy under hydrothermal conditions. The magnetic properties of 2 and 3 were investigated‥

Two ideal triangular Ni3 compounds [Ni3(μ1,3-N3)3(2,2′-bpy)3]X3·3H2O (X = ClO4- (1) and BF4- (2); 2,2′-bpy = 2,2′-bipyridine) have, for the first time, been structurally and magnetically characterized, and represent a good model for us to understand the magnetic behaviours in extended azide-bridged nickel(II) complexes with trinuclear subunits.

The three-dimensional chiral helical framework of the four-coordinate zinc complexes, [Zn(bdt)]n (1a and 1b) (H2bdt = 1,4-benzeneditetrazol-5-yl), has been prepared via hydrothermal reaction. At the chiral centers, the tetrahedral zinc centers link with bdt ligands to form a chiral unc-type network, which exhibits an intense blue emission and spontaneous chiral resolution. The enantiomers of 1a and 1b have been confirmed by solid-state circular dichroism spectra.

A novel three-dimensional (3D) nanoporous metal–organic framework with moganite topology, [Co2(ox)2(dchtpy)]n·9nH2O (1·9H2O), has been obtained from the hydrothermal reaction of CoCl2, oxalic acid, NaOH and 1a,4a-dihydroxy-1e,2e,4e,5e-tetra(4-pyridyl)cyclohexane (dchtpy). X-ray analysis reveals that the bulky dchtpy ligands link four adjacent metal oxalate chains and form a 3D hybrid network with both moganite topology and 3D channels in various sizes. The largest pores (channel A) are the ones viewed along the a-axis, which are composed of two [Co(ox)]n chains and two bulky ligands in the dimensions of 10.76 × 10.67 A excluding the van der Waals radii. Along the {101} direction there was found the second large channels (channel B) in the size of 10.51 × 4.66 A. Notably the hydroxyl groups of dchtpy extend towards the channels on the middle of the walls, dividing the pores with two small channels in approximately 4.50 × 4.66 A. Besides, small pores in dimensions of 7.07 × 8.24 A and 6.98 × 6.06 A can also be found along the a- and c-axes, respectively. The potential solvent accessible void of the framework, calculated by PLATON, is 46.1% of the total volume and is occupied with disordered aqua molecules. Variable-temperature powder X-ray diffraction experiments confirmed that the crystallinity and network integrity of 1 can be retained up to 375 °C upon the removal of guest aqua molecules, in which thermal stability is among the most stable metal organic coordination frameworks. The framework shows guest-induced dynamic flexibility and elasticity and has a gating effect on the sorption of small gas molecules. The hydroxyl groups from the ligands functionalize the walls of the channels and have strong hydrogen bonds with adsorbents, leading to high sorption capacity at ambient temperature. Magnetic studies revealed significant antiferromagnetic interaction between the Co(II) ions in 1·9H2O with J = −12.4(1) cm−1 and g = 2.450(4).

Two kinds of water clusters, the unique dodecahedral (H2O)14 cage and the truncated cubic (H2O)12 cluster formed from both coordinated and lattice water molecules, are captured in three lanthanide complexes [Ln4(chtc)3(H2O)10]·9H2O (Ln = Tb 1, Yb 2, Dy 3, H4chtc = cyclohexane-1,2,4,5-tetracarboxylic acid). Compound 1 exhibits the characteristic photoluminescence of the Tb3+ ion in the visible region, while 2 exhibits NIR luminescence properties.

The unique tetrapyridyl ligand 1,2,4,5-tetra(4-pyridyl)benzene (bztpy) isolated from previous hydrothermal in situ metal ligand reaction is found to exhibit remarkable anion-dependent assembly of a series of novel metal–organic frameworks (MOFs), [Cu2(CN)2(bztpy)] (1), [Cu(SO4)(bztpy)]·1.5H2O (2), [Cu2Br2(bztpy)]·MeCN (3) and [Cu10I10(bztpy)2]·2H2O (4), which were synthesized under hydro/solvothermal conditions. These MOFs were characterized by elemental analysis, IR and single-crystal X-ray diffraction. Compound 1 consists of [Cu(CN)]n chains that link the neighbouring ones via tetradentate bztpy bridges to form a corrugated 2D layer. When bztpy is treated with CuSO4, a 3D (3,5)-connected network 2 is obtained, in which novel [Cu(bztpy)]n ladders are interconnected by sulfate anions μ-bridges. However, Br− and I− anions assist the formation of {Cu2Br2} and {Cu10I10} SBU in the cluster-based metal–organic frameworks 3 and 4, respectively, and result in a completely different topology. Compound 3 shows a 3D PtS net, while compound 4 has a new 3D (4,8)-connected topology. A discussion of the crystal structures, as well as the coordination behaviour of the special tetrapyridyl ligand upon different geometries of the central connecter is provided. In addition, the photoluminescent properties of 1, 3 and 4 in the solid state at ambient temperature are also investigated.

Five new complexes were obtained from solution or hydrothermal reactions of M(OAc)(2) (M = Mn, Cu and Cd) or CuCl(2) with 4-amino-3,5-bis(pyridin-2-yl)-1,2,4-triazole (abpt) and NaN(3) or 1,3,5-benzenetricarboxylic acid (btcH(3)) in different molar ratios. Structural analysis reveals that Cd(abpt) units in [Cd(abpt)(mu(1,1)-N(3))(2)](n) (1) are bridged by double mu(1,1) end-on (EO) azides into 1D zigzag coordination chains. Similar structural motifs, i.e. the chelation of abpt to the metal center and the double bridges of EO azides, are found in [Mn(4)(abpt)(4)(mu(1,1)-N(3))(8)(H(2)O)(2)] (2). The terminal aqua molecules and the monodentate N(3)(-) groups lead to the formation of a tetranuclear complex rather than a polymeric compound. The abpt underwent deamination in the presence of copper ions during the process of coordination and became 3,5-bis(pyridin-2-yl)-1,2,4-triazolate (bpt-H) in 3-5. [Cu(4)(bpt-H)(4)(N(3))(4)].4.5H(2)O (3) is a neutral tetranuclear grid-like complex, in which the azides act as monodentate ligands. A similar [Cu(4)(bpt-H)(4)](4+) grid-like unit was found in [Cu(4)(bpt-H)(4)(mu-btcH)Cl(2)].2H(2)O (4) and a pair of symmetry-related copper atoms are bridged by the mu-btcH(2)(-) coligand in a butterfly-shaped structure. In [Cu(2)(bpt-H)(mu(6)-btc)(H(2)O)](n) (5), the tetranuclear {Cu(4)(mu-bpt-H)(2)(mu(3)-carboxylate)(2)}(4+) units are bridged by mu(6)-btc(3-) ligands in a 2D step-like layer structure. Temperature-dependent magnetic susceptibility measurements reveal that the double mu(1,1)-N(3)(-) bridges in 2 transmit the ferromagnetic interactions between Mn(2+) centers (J(1) = J(2) = +3.09(4) cm(-1), g(Mn(II)) = 2.02(1)), and the mu-(bpt-H)(-) bridges transmit moderate antiferromagnetic interactions in both 3 (J = -12.78(13) cm(-1)) and 4 (J(1) = -14.96(11) cm(-1)). In 4 the antiferromagnetic coupling via the mu-btcH(2-) bridge was found as the second coupling pathway (J(2) = -9.48(7) cm(-1)). The coexistence of ferromagnetic and antiferromagnetic coupling between four Cu(2+) centers occurs in 5 (J(1) = -0.88(3) cm(-1) and J(2) = +5.01(2) cm(-1)). The magneto-structural relationship for tetranuclear copper pyrazolate/triazolate compounds has been discussed.

Two new hybrid inorganic-organic frameworks containing perfluorinated dicarboxylate ligands have been synthesized ionothermally from a mixture of 1-ethyl-3-methylimidazolium bromide (emim-Br), and triflimide (emim-Tf(2)N). The cobalt(ii) tetrafluorosuccinate, [emim](2)[Co(H(2)O)(2)(O(2)CCF(2)CF(2)CO(2))(2)] (), is a two-dimensional coordination polymer containing anionic framework layers separated by emim cations. When hexafluoroglutaric acid is used in similar reactions, [emim](2)[Co(3)(O(2)CCF(2)CF(2)CF(2)CO(2))(4)(H(2)O)(4)] () forms. Like , this phase contains anionic layers of cobalt and the fluorinated carboxylate separated by emim cations. These new phases represent the first examples of ionothermally synthesized materials using perfluorinated aliphatic carboxylates.

Spontaneous resolution of mandelic acid occurred upon coordination via stereochemical control on the metal centres. The ‘ideal’ octahedral coordination geometry with bis-chelation in cis-conformation is critical for chiral discrimination. The successful induction of homochiral packing of the mandelates by five different metals suggests general applicability of stereochemical control on the resolution of the chiral organic compounds.

Ionothermal synthesis using a deep eutectic solvent has been used for the first time to prepare a borate-containing material. The metallophosphate-borate compound crystallises in chiral space group I222. Two different alkyl ammonium cations derived from the ionic liquid have distinct template effects on the formation of cobalt phosphate layers and hydrophobic borate channels.

Seven 3-D (3D) metal–organic framework solids [Nd2(pyta)2(H2O)6]n1 and {[Ln2(pyta)2(H2O)x]·yH2O}n (Ln = Sm 2, Eu 3, Gd 4 with x = 3, y = 2.5; Ln = Tb 5 with x = 2, y = 2.5, Ln = Dy 6, Ho 7 with x = 2, y = 2), H3pyta = 2,4,6-pyridinecarboxylic acid) have been prepared under hydrothermal conditions. X-Ray structural analysis shows that compound 1 crystallises in monoclinic space groupPc and all Ln(III) ions are nine-coordinated. The 3D framework of 1 is constructed from [Nd4(µ4-pyta)2]n chains with 1D small channels along the a axis. Isomorphous compounds 2–7 crystallise in C2/c space group and are composed of alternative [Ln4(µ5-pyta)2]n chains and [Ln6(µ4-pyta)2]n helical chains. The completely deprotonated pyta3− ligands adopt µ4-bridging coordination modes in 1, and µ4-, µ5-bridging modes in 2–7. The Sm(III) 2, Eu(III) 3, Tb(III) 5 and Dy(III) 6 compounds exhibit characteristic photoluminescence (PL) in the visible region and the Nd(III) 1 and Ho(III) 7 compounds show photoluminescence in the near-infrared (NIR) region. The magnetic properties of three heavy lanthanide ions Gd(III) 4, Dy(III) 6 and Ho(III) 7 compounds were investigated in the temperature range of 2–300 K.