Two cobalt(II) compounds, namely, {[Co(HL)(bpy)(H2O)2]·DMF}n (1), and {[Co(HL)(bpe)]·0.5bpe}n (2) (H3L = 1,3-bis(2-carboxylphenoxy)benzoic acid, bpy = 4,4′-bipyridine, bpe = 4,4′-vinylenedipyridine), have been synthesized using cobalt(II) transition metal salt with phenolic carboxylic acid and different N-donor ligands. The compounds were fully characterized by elemental analysis, infrared spectroscopy (IR), single crystal X-ray diffraction analysis, and thermogravimetric analysis (TGA). Both compounds exhibit 2-D (4,4)-sql networks but with a wavelike and a double layered arrangement, respectively. Remarkably, these two compounds not only exhibit field-induced single-ion relaxation magnetization but also exceptional catalytic activities of benzylic C–H oxidation (conv. 90.3–99%; sele. 98.1–99%).

Two copolymers of P1 and P2 comprising benzothiadiazole, 1,4-bis(dodecyloxy)-benzene units were synthesized by Sonogashira coupling polymerization based on ethynyl-linked 1,2,5,6-naphthalenediimide. Their thermal, optical, electrochemical as well as charge transport properties were studied. Bottom-gate top-contact organic field-effect transistors (OFETs) measurements of P1 and P2 thin films showed different charge transport behaviors. P1 displayed pure electron transport behaviors in OFETs with electron mobility up to 10−3 cm2·V−1·s−1, while P2 exhibited hole transport features. The molecular structure analysis revealed that the structure of P1 has the acceptor-linker-acceptor′ (A-L-A′) characteristic, and P2 possesses the donor-linker-acceptor (D-L-A) structure feature. The results demonstrate that different molecular structures lead them to have distinct charge transport behaviors. In particular, the first pure electron transport copolymer in OFETs based on 1,2,5,6-naphthalenediimide is achieved.

•Two helical Eu(III) metal-organic frameworks were solventhermally synthesized in different solvents.•Both complexes can sensitively and selectively detect nitrobenzene and Cu2+ ions.•The mechanism of sensing properties were discussed in details.Two helical Eu(III) metal-organic frameworks, namely, {[Eu(L)(DMF)(H2O)]·0.5DMF}n (1) and [Eu(L)(DEF)(H2O)]n (2) (H3L=3,5-bis(2-carboxylphenoxy)benzoic acid, DMF=N,N-dimethylformamide, DEF=N,N-diethylformamide), have been solvothermally synthesized in different solvents, respectively. Both complexes possess helical structures through the connectivity of Eu atoms and phenolic-oxygen containing branches of the flexible multicarboxylate ligand. Based on different helices, these two complexes exhibited hexagonal and tetragonal channels, respectively. Both complexes possess (3,6)-connected (4.62)2(42.610.83) topology but with different long Schlafli symbol. The solvent plays an important role in the formation of the final frameworks. Both complexes can sensitively and selectively detect nitrobenzene and Cu2+ ions.Two helical Eu(III) compounds were synthesized from a phenolic multicarboxylate ligand, showing fluorescence sensing towards nitrobenzene and Cu2+ ions.Download high-res image (333KB)Download full-size image

The mixed 3d–4f pentanuclear complex (Bu4N)[MnIII4YIII(shi)4(OAc)4(CH3OH)4]·CH3OH·H2O (1) (H3shi = salicylhydroxamic acid) was synthesized by the direct reaction of Y(NO3)3·6H2O, Mn(OAc)2·4H2O, and H3shi. When an additional ligand, (NHBu3)3[W(CN)8]·2H2O, was added, the mixed 3d–4f–5d hexanuclear complex (Et4N)5[MnIII4YIII(shi)4(OAc)4WV(CN)8](WO4)0.5 (2) was obtained. X-ray crystallographic analysis shows that the 3d–4f complex 1 represents a 12-metallacrown-4 (12-MC-4) structure, in which the metallacrown ring [Mn–N–O]4 connection captures one YIII ion with four bridging acetate anions, completing the eight-coordinated environment around YIII ion, while four methanol molecules each coordinate to the MnIII ions on the other side of the YIII ion. After octacyanotungstate is introduced, the [WV(CN)8] group substitutes for four methanol molecules of 1 to form complex 2. Magnetic studies indicate the overall antiferromagnetic coupling present within the MC ring of complex 1. However, interestingly, the dominant ferromagnetic coupling between MnIII ions was observed in complex 2. A susceptibility analysis shows that the natural spin alignments in 12-MC-4 metallacrowns are tuned from overall antiferromagnetic to dominant ferromagnetic fashions by magnetic coupling between MnIII ions and the WV ion. Complex 1 [MnIII4YIII] retains an S = 0 ground state, and complex 2 [MnIII4YIIIWV] shows obvious single-molecule magnet (SMM) behavior with an ST = 11/2 ground state, respectively, before and after introduction of the octacyanotungstate group. The spin frustration geometrical structure constructed by four MnIII ions and one WV ion was considered as the key factor for switching on the SMM properties of the 12-MC-4 system.

Six metallacrown complexes {La(OAc)(H2O)2[15-MCCu(N)glyha-5](H2O)4}·2NO3·5H2O (1), {Gd(OAc)(H2O)[15-MCCu(N)glyha-5](H2O)3}·2NO3·5H2O (2), {Tb(OAc)(H2O)[15-MCCu(N)glyha-5](H2O)4}·2NO3·4H2O (3), {Pr(NO3)(H2O)2[15-MCCu(N)glyha-5](H2O)}·2NO3·8H2O (4), {Nd(NO3)(H2O)2[15-MCCu(N)glyha-5](H2O)2}·2NO3·7H2O (5) and {Sm(NO3)(H2O)2[15-MCCu(N)glyha-5](H2O)2}·2NO3·6H2O (6) (glyha2− = dianion glycinehydroxamic acid) have been synthesized and structurally characterized by X-ray single crystal diffraction, IR spectroscopy and elemental analysis. Spectroscopic studies show that these complexes bind to CT-DNA via an intercalative mode and cause a more B-like to a more C-like conformational change. Magnetic measurements indicate that complexes 1, 3, 4, 5 and 6 dominantly show antiferromagnetic interactions between metal centers, whereas complex 2 reveals ferromagnetic interactions.

An unusual solvent effect on the synthesis of five manganese complexes [Mn2(L1)2(Py)4](1), [Mn2(L1)2(DMSO)4](2), [Mn4(L2)4(OH)4](3), [Mn4(L3)2(DMSO)7(H2O)](4), and [Mn6O2(L4)4(OAc)2(OMe)2(DMSO)4]·MeOH] (5), (H3L1 = 5-(2-oxyphenyl)-pyrazole-3-carboxylic acid; H2L2 = 5-(2-oxyphenyl)-pyrazole-3-carboxylic acid amide; H4L3 = di-[5-(2-oxyphenyl)-pyrazole]-3-hydroxamic ether; and H2L4 = 5-(2-oxyphenyl)-pyrazole-3-carboxylic acid methyl ester) has been reported. Five complexes have been characterized by X-ray single crystal diffraction, IR, element analysis, thermogravimetric analysis and UV-vis spectra. The analysis reveals that complexes 1 and 2 are isostructural with a bimetallic six-membered ring and L1 from the decomposition of the original H4ppha (H4ppha = 5-(2-hydroxyphenyl)-pyrazole-3-hydroxamic acid) ligand. Complexes 3 and 4 are two tetranuclear clusters, and 3 possesses an aza12-metallacrown-4 core with L2 from the amide functionalization of the decomposition L1; while 4 represents a novel linear [Mn4N8O2] core with L3 from the condensation of L1 and H4ppha. Complex 5 is the first Mn6 cluster linked by two stacked, off-set 8-azametallacrown-3 subunits with [M–N–N–M–N–N–M–O] connectivity, and L4 derived from the esterification of L1. The magnetic behaviour of complexes 1–5 show the dominant antiferromagnetic interactions between metal centers, whereas complex 5 further reveals the coexistence of antiferromagnetic and ferromagnetic interactions, and slow magnetic relaxation at T < 6 K with S = 4 ground state, as well as field induced magnetization saturation.

Reaction of Mn(OAc)2·4H2O with the H2L ligand affords a new manganese 22-MC-8 azametallacrown [Mn8(μ3-O)2(μ3-OH)2(μ2-OH)2(L)6(OAc)2(OH2)4]·2DMF (H2L = 3-(2-oxyphenyl)-5-(pyrazin-2-yl)-1,2,4-triazole). The structural analysis of the complex reveals that the azaMC ring possesses –[Mn–O–Mn–N–N–Mn–N–N–Mn–N–N]– connectivity. The magnetic behavior of the complex shows the dominant antiferromagnetic interactions between the manganese ions with S = 4 and the frequency-dependent out-of-phase signal.

Two novel electrochromic monomers, 4,7-bis(4-methoxythiophen-2-yl)-[1,2,5]thiadiazolo[3,4-c]pyridine (MOTTP) and 4,7-bis(4-butoxythiophen-2-yl)-[1,2,5]thiadiazolo[3,4-c]pyridine (BOTTP), were synthesized and electropolymerized to give the corresponding polymers PMOTTP and PBOTTP, respectively. For the investigation of their electrochemical and electrochromic properties, the polymers were characterized using cyclic voltammetry (CV), UV-vis spectroscopy, step profiling, and scanning electron microscopy (SEM). The band gaps of the polymers were calculated based on spectroelectrochemical analysis, and were found to be 0.950 eV and 1.088 eV for PMOTTP and PBOTTP, respectively. Electrochromic investigations showed that PMOTTP and PBOTTP showed similar multichromic behaviors: saturated green color in the neutral state, highly transmissive blue in the oxidized state, and saturated red in the reduced state (red-green-blue, RGB). In addition, both polymers have excellent switching properties with more than 60% optical contrast in the NIR region and about a 0.5 s response time from neutral to oxide. Moreover, via electrochemical and spectral analyses both polymers were proven to be n-type dopable polymers. Hence, both polymers are promising materials to complete RGB electrochromic polymers for commercial applications.

An isomorphous family of mixed 3d–4f dodenuclear aggregates, {[MnIII8Ln4(Clshi)8(OAc)6(μ3-OCH3)2(μ3-O)2(CH3OH)12(H2O)2]·4CH3OH·xH2O)} (where Ln = EuIII (1), GdIII (2), TbIII (3), and DyIII (4); ClshiH3 = 5-chlorosalicylhydroxamic acid; x = 5 for 1 and 3; x = 6 for 2; x = 2 for 4), were synthesized and characterized. They were obtained from the reaction of ClshiH3 with Mn(OAc)2·4H2O and Ln(NO3)3·6H2O. These isomorphous mixed 3d–4f compounds represent a family of novel structures with lanthanide ions in the metallacrown (MC) ring. Each dodecanuclear aggregate contains two offset stacked 14-MC-5 units with M–N–O–M–N–O–Ln–O–N–M–O–N–M connectivity to capture one LnIII ion in the core of each MC. Two 14-MC-5 units are connected through O ions with four Mn ions and six O atoms arranged in a double Mn4O6 cubane. Magnetic measurement indicates that antiferromagnetic interactions are present between the metal ions. The DyIII analogue with high anisotropy and large spin shows slow magnetization relaxation at a direct-current field of 2 kOe.

Hydrothermal reactions of aromatic 3,3′,5,5′-biphenyltetracarboxylic acid (H4bpt) and the transitional metal cations in the presence of rigid or flexible N-donor ancillary ligands afford nine novel coordination polymers, namely, [M(H2bpt)(Hpptp)]n (M = Mn (1), Fe (2), Co (3), and Zn (4)), [Mn2(bpt)(Hpptp)2]n (5), {[Zn3(Hbpt)(bpt)(H2O)2][(4,4′-H2bmib)0.5]·H2O}n (6), {[Cu(bpt)0.5(4,4′-bimbp)]·H2O}n (7), {[Co(H2bpt)(2,7-dfo)]·H2O}n (8), and {[Ni2(bpt)(4,4′-bibp)2.5(H2O)]·3(H2O)}n (9) (Hpptp = 2-(3-(4-(pyridin-4-yl)phenyl)-1H-1,2,4-triazol-5-yl)pyridine; 4,4′-bmib = 4,4′-bis(2-methylimidazol-1-yl)benzene; 4,4′-bimbp = 4,4′-bis(imidazol-1-ylmethyl)biphenyl; 2,7-dfo = 2,7-di(imidazo-1-ly)-9H-fluoren-9-one; 4,4′-bibp = 4,4′-bis(imidazol)biphenyl). Their structures have been determined by single-crystal X-ray diffraction analyses, elemental analyses, IR spectra, powder X-ray diffraction (PXRD), and thermogravimetric (TG) analyses. Complexes 1–4 are isomorphism and feature a similar 2-fold interpenetrating 2D helical double layer, which is further extended via the interlayer π···π interactions into a 3D supramolecular structure. Complex 5 displays a pillared-layer 3D porous network with a (62.8)2(62.82.102) topology. Compound 6 shows an unprecedented 3D host-framework consisting of Zn6 clusters and exhibits a novel 3D (5,5,5,6,9)-connected topological net with the Schläfli symbol of (410.65)(419.616.8)(46.64)(47.63)2. The topology of 7 is an unprecedented binodal (4,4)-connected 3D network with the Schläfli symbol of (62.84)(42.82)2. Complex 8 exhibits a 3D (66) structure with left- and right-handed helical chains arranged alternately. Complex 9 is a novel trinodal (4,4,5)-connected 3D framework with the Schläfli symbol of (64.82)(65.8)(68.82). To the best of our knowledge, the 3D frameworks with (5,5,5,6,9)-connected net for 6, binodal (4,4)-connected for 7, and trinodal (4,4,5)-connected for 9 have never been documented to date. Moreover, the luminescent properties of 4 and 6 have been investigated.

Two genuine supramolecular isomers of Cd(II) coordination polymers with an identical formula of [Cd(pptp)(ox)]n (1a and 1b) (pptp = 2-(3-(4-(pyridin-4-yl)phenyl)-1H-1,2,4-triazol-5-yl)pyridine, H2ox = oxalic acid) have been hydrothermally synthesized and characterized. Both compounds possess the rod-like binuclear [Cd2(pptp)2] subunit, which are linked by the ox ligand to afford either a flat or wavy two-dimensional (2D) 63-hcb network, depending upon whether the additive agent is used for the reaction. The photoluminescence behaviour of the compounds was also discussed.

Solvothermal reactions of aromatic quaterphenyl-2,5,2′,5′-tetracarboxylic acid (H4qptc) ligand and transitional metal cations of MII (M = Co, Ni, Mn, Cu, Zn) in the presence of 1,10-phenanthroline (phen) afford five new coordination polymers (CPs), namely, {[M(H2qptc)(phen)(H2O)2]·2H2O}n (M = Co (1), Ni (2)), [Mn(qptc)0.5(phen)(H2O)]n (3), [Cu(qptc)0.5(phen)]n (4) and [Zn3(Hqptc)2(phen)2(H2O)2]n (5). Their structures have been determined by single-crystal X-ray diffraction analyses and further characterized by elemental analyses, IR spectra, powder X-ray diffraction (PXRD) and thermogravimetric (TG) analyses. Complexes 1 and 2 are isostructures and each displays a one-dimensional (1D) zigzag chain, which further forms a 2D supramolecular architecture via inter-chain π⋯π interactions. Complex 3 possesses a (3,6)-connected CdI2 layered architecture incorporating left- and right-handed helical chains. Complex 4 exhibits a 3D porous structure with rare (3,6)-connected ant topology. Complex 5 shows a 3D (3,4,5)-connected network with (42.6)2(43.62.8)(45.64.8)2 topology. The results show that the conformations and coordination modes of H2qptc2−/qptc4− ligand are crucial factors for the formation of the different structures. Moreover, the photoluminescence of 5 has been investigated.

Five novel compounds, {[Ni(PA)(bpe)(H2O)2]·DMF}n (1), {[Zn(PA)(bpe)]·DMF}n (2), {[Zn(PA)(bpe)]·2DMF·CH3OH}n (3), {[Cd2(PA)2(bpe)2(H2O)]·3.5H2O}n (4), {[Ni2(PA)2(bpp)2(H2O)3]·2DMF}n (5), based on pamoic acid (H2PA) (bpe = 1,2-bi(4-pyridyl)ethane, bpp = 1,3-bi(4-pyridyl)propane) have been synthesized. In such a system, both the PA2– anion ligand and dipyridyl ligands act as bipodal linkers, connecting the metal centers in square or tetrahedral geometries into 4-connected topologies with different entangled modes: 3-fold interpenetrating CdSO4 net (65.8) (1), roto-translational [2 + 2] interpenetrating diamond pseudosupramolecular isomers (2 and 3), 3-fold interpenetrating (6.74.8)(64.7.8) (4) and (6.85)(64.82) net with both 2-fold interpenetrating and self-penetrating characters (5), respectively. The formation of unique penetrating frameworks was investigated in detail. Gas adsorption and photoluminescent properties of the compounds have also been explored.

Crystallization of a Schiff base with nickel acetate in different solvents yields a tetranuclear (dicubane-like [Ni4O4] core with two missing vertices) and a hexanuclear cluster ([Ni6O6] core with two nickel(II) ions attached to a [Ni4O4] cubane through oxygen bridges). Metal centers within these clusters exhibit ferromagnetic and antiferromagnetic coupling interactions, respectively.

A novel coordination polymer [Co(bpbc)(H2O)2]n (1) was synthesized by hydrothermal reaction of Co(OAc)2·2H2O and 2,2′-bipyridine-4,4′-dicarboxylate acid (H2bpbc). X-ray single diffraction studies reveal that compound 1 exhibits chiral two-fold interpenetrating 3-D network, which contains different numbers of left- and right-handed helical chains. The magnetic property is also investigated.An unusual chiral interpenetrating coordination polymer is synthesized by rigid organic ligand, which contains different numbers of left- and right-handed helical chains.Highlights► Rigid bifunctional ligand was used to construct chiral interpenetration coordination polymer. ► This chiral coordination polymer is constructed by different numbers of left- and right‐handed helical chains. ► Antiferromagnetic coupling dominating the magnetic properties.

A novel enneanuclear manganese complex, [Mn9O4(Mesao)6(MeO)3(O2CMe)3(OH)(MeOH)2]·2.5DMF [1; Me-saoH2 = 2-hydroxyphenylethanone oxime], was synthesized. The structure of 1 contains an unusual [Mn9O4] core with an unprecedented defective “supertetrahedron” topology based on two parallel, onset stacked 9-MC-3 and 15-MC-6 metallacrown subunits. Magnetic studies indicate that 1 behaves as a single-molecule magnet.

Six complexes based on a flexible tripodal ligand H3TTTA (2,2′,2″-[1,3,5-triazine-2,4,6-triyltris(thio)]tris-acetic acid) have been hydrothermally synthesized and structurally characterized. X-ray single-crystal diffractions reveal that they have rich structural chemistry: mononuclear, [Zn(HTTTA)(2,2′-bpy)(H2O)3]n (1); dimeric metallamacrocycle, [Zn(HTTTA)(2,2′-bipy)(H2O)]n (2) and [Cd(HTTTA)(2,2′-bipy)(H2O)·H2O]n (3); two-dimensional networks with binodal (3,6)-connected CdI2 topology based on linear trinuclear M3(μ2–CO2)4(μ2–CO2)2 SBUs (Secondary Building Units), [M3(TTTA)2(2,2′-bipy)2(H2O)m·nH2O]n (M=Zn·4, m=0, n=4; Cd·5 and Mn·6, m=2; n=2). The value of pH and the metal ions has large influences on the resulting structures. The flexible tricarboxylic acid exhibits four coordination modes from monodentate to μ6-bridge. Fluorescence and magnetic properties of the complexes have also been investigated in details.Graphical abstractSix complexes based on a flexible tricarboxylate ligand exhibit rich structural chemistry from mononuclear to 2D (3,6)-connected networks. PH and metal ions have large influences on the resulting structures.Highlights► Six complexes based on a flexible multicarboxylate ligand have been reported. ► They exhibit diverse structures from mono- and binuclear molecules to 2-D layers. ► pH and metal ions have large influences on the final products.

Five new complexes, [Co3(HL1)2(Py)8]·4CH3OH (1), [Ni3(HL1)2(Py)4]2·2DMF (2), [Co3(H2L2)2(Py)8]·2NO3 (3), [Ni2(HL2)(Py)6] (4) and [Cu4(HL2)2(Py)4]·4DMF (5) (H4L1 = N-propionyl-4-hydroxysalicylhydrazide, H44-hopshz; H5L2 = N-(3-carboxy-cis-2-propenoyl)-4-hydroxysalicylhydrazide, H54-hocpshz) have been obtained from two N,N′-diacylhydrazide ligands and characterized by elemental analysis, FT-IR, X-ray diffraction and antimicrobial activities. These di-, tri-, and tetrameric complexes are connected into three-dimensional supramolecular architectures with interesting topologies through O–H⋯O, C–H⋯O and C–H⋯π interactions. 1–3 are linear trimeric complexes with the ligands triply-deprotonated. Topological analysis indicates that they exhibit 2D (4,4), 3D (6,8)-connected (3349526)(3441257647) and 8-connected (42563) net, respectively. 4 and 5 possess dimeric and tetrameric structures, which are extended into 7-connected (33413536) and 4-connected (4,4) net, respectively.Based on two different N,N′-diacylhydrazides by changing the terminal groups from propionyl to 3-carboxy-cis-2-propenoyl, we have obtained five transition metal complexes with polynuclear structures. Two ligands exhibit diverse coordination modes due to the deprotonation and flexibility as well as different coordination geometry of metal centers. Through different O–H⋯O, C–H⋯O and C–H⋯π weak interactions, novel supramolecular nets are obtained.

Solvothermal synthesis method has been successfully introduced into the diphosphine carborane system, and two new nickel complexes containing nido-carborane diphosphine ligand [7,8-(PPh2)2-7,8-C2B9H10]− with the formula [Ni2(μ-Cl)(μ-OOPPh2){7,8-(PPh2)2-7,8-C2B9H10}2]·CH2Cl2 (1) and [H3O][NiBr2] {7,8-(PPh2)2-7,8-C2B9H10}·C6H6 (2) were obtained by the reactions of 1,2-(PPh2)2-1,2-C2B10H10 with NiCl2·6H2O or NiBr2·6H2O in CH2Cl2 under the solvothermal condition. Both of the two complexes have been characterized by the elemental analysis, FT-IR, 1H and 13C NMR spectroscopy and single crystal X-ray diffraction. The X-ray structure analysis for these two complexes reveals the nido-nature of the carborane diphosphine ligand, indicating that the solvothermal synthesis is an efficient method for the degradation of the closo-carborane diphosphine ligand.

An efficient synthesis of trisubstituted alkenes including 1,2-heterodisubstituted alkenes has been described. Reactions of thiols and amines with 1,1-dibromo-1-alkenes in the presence of TBAF·3H2O afford (Z)-2-bromovinyl sulfides and (Z)-2-bromovinyl amines regio- and stereoselectively. The reaction proceeds under catalyst-free conditions with high efficiency. The coupling reactions of the obtained products bearing bromine atoms with phenylacetylene and phenylboronic acid gave trisubstituted alkenes in good to excellent yields. Cross-coupling with various N, O, S, and P nucleophiles selectively generated 1,2-N,O, 1,2-N,S, 1,2-S,P, 1,2-S,S, and 1,2-S,O heterodisubstituted alkenes.

A tetranuclear manganese complex, [Mn4(hmp)6(N(CN)2)4(H2O)2] [1; Hhmp = 2-(hydroxymethyl)pyridine; N(CN)2− = dicyanamide anion], was synthesized and characterized by single-crystal X-ray diffraction, bond valence sum calculations, IR spectra, elemental analysis, and magnetic measurements. The structure of 1 consists of a linear [MnII2MnIII2] core formed by six hmp− groups linking MnII/III ions. Magnetic studies show that 1 behaves as a single-molecule magnet with ferromagnetic coupling between the metal centers.

A mixed-type of azametallacrown based on a flexible pentadentate N-propionyl ligand was reported, which exhibits not only the completely different arrangement of the metal centers but also diversely geometric configurations of the N-terminal ligands, and this complex can further assemble into a novel 3-D supramolecular structure using two different aza18-MC-6 as secondary building units (SBUs) via the intermolecular C–H⋯π, π–π and C–H⋯O interactions. Temperature-dependent magnetic susceptibility measurements of the title complex indicate that the complex presents significantly antiferromagnetic coupling among metal centers.An unprecedented mixed-type of azametallacrown based on a flexible pentadentate N-propionyl end ligand was reported, which exhibits not only the completely different arrangement of the metal centers but also diverse geometric configurations of the N-terminal ligands, and which was further assembled into novel 3-D supramolecular structure via various intermolecular interactions.

An 18-membered complex, [Fe(MMSHZ)(DMF)]6 (1) [MMSHZ = N-(methyl-maleamic ester)acylsalicylhydrazine] was synthesized and structurally characterized. There are not only particular geometry configurations of N-terminal groups which result in the unique shape of the centric cavity, but also inter- and intra-molecular interactions assembling adjacent molecules into 2-D framework in complex 1. Temperature-dependent magnetic susceptibility measurements indicate that this complex exhibits significantly antiferromagnetic coupling among the metal centers.An 18-membered complex, [Fe(MMSHZ)(DMF)]6 (1) [MMSHZ = N-(methyl-maleamic ester)acylsalicylhydrazine] was reported. The complex 1 exhibits not only unique coordination configurations of N-terminal groups resulting in the particular shape of the cavity in complex 1, but also inter- and intra-molecular interactions assembling this complex into the first 2-D framework via intermolecular EF stacking interactions and C–H⋯O hydrogen-bond interactions.

Three 12-metallacrown-4(12-MC-4) organotin(IV) complexes [12-MC[RSn(IV)]N(shi)-4] (R = Et(1), Bu(2), Ph(3); Shi = salicylhydroxamic acid) have been synthesized and characterized by elemental analyses, IR, TGA and X-ray diffraction. Single-crystal X-ray analyses reveal that all the complexes 1–3 contain a neutral 12-membered metallacrown ring which is formed by the succession of four repeating units of –[Sn–N–O]–. The metallacrown molecules of complexes 1 and 2 are further linked by intermolecular C–H···O interactions to form a 2D supramolecular networks, while the molecules of complex 3 are linked by intermolecular C–H···O and C–H···π interactions to form a 3D framework.Three 12-MC-4 organotin(IV) complexes [12-MC[RSn(IV)]N(shi)-4] (R = Et(1), Bu(2), Ph(3); Shi = salicylhydroxamic acid), which are the novel example of organotin(IV) metallacrowns, have been synthesized and characterized by elemental analyses, IR, TGA and X-ray diffraction.

Three dinuclear copper(I) complexes with the formula [Cu2(μ-X)2(1,2-(PiPr2)2-1,2-C2B10H10)2] (X = Cl (1), Br (2), I (3)) containing the closo carborane diphosphine ligand 1,2-(PiPr2)2-1,2-C2B10H10 have been prepared and characterized by elemental analysis, FT-IR and X-ray structure determination. The X-ray structure analyses revealed that the three complexes were isostructural and crystallized in the monoclinic system and space group C2/m. The carborane cage ligand was coordinated bidentately to the Cu(I) center through its two phosphorus atoms, and the coordination geometry around each copper atom was distorted tetrahedral. Two halogen atoms bridged the metal centers forming a dimer structure [Cu2(μ-X)2(1,2-(PiPr2)2-1,2-C2B10H10)2], which were linked into 2D supramolecular networks through novel C–H⋯H–B dihydrogen bonding interactions.

Reactions of (NH4)2MS4 or (NH4)2MOS3 (M = Mo, W) with AgSCN and closo carborane diphosphine ligand 1,2-(PPh2)2-1,2-C2B10H10 (L) in CH2Cl2 yielded four heterobimetallic trinuclear Mo(W)–Ag–S clusters: [Ag2MoS4L2] (1), [Ag2WS4L2] (2), [Ag2MoOS3L2] (3) and [Ag2WS4L2] (4), respectively. All the new clusters have been characterized by elemental analysis, FT-IR, UV–Vis, 1H and 13C NMR spectroscopy and their molecular structures (except for 3) were further confirmed by single-crystal X-ray diffraction. X-ray crystal structure analysis showed that the closo carborane diphosphine ligand was coordinated bidentately to Ag(I) atom through its two phosphorus atoms, resulting in a stable five-member chelating ring between the diphosphine ligand and the metal. The coordination sphere of the central M atom, as well as all the Ag atoms, was tetrahedron. The skeletons of these clusters could be classified into two types: with (NH4)2MS4, the three metal atoms (two Ag atoms and one M atom) are in a linear conformation, while with (NH4)2MOS3, the conformation of the heterobimetallic trinuclear cluster is butterfly shaped. The luminescence properties of the clusters were investigated in CH2Cl2 solution at room temperature and for the first time the butterfly-shaped Ag–W–S cluster containing the Ag2WS4 core has been proved to show luminescence property.The closo carborane skeleton was introduced into the system of the heterometallic sulfide clusters and four heterobimetallic trinuclear Mo(W)–Ag–S clusters with linear or butterfly-shaped skeleton containing 1,2-bis(diphenylphosphino)-1,2-dicarba-closo-dodecaborane have been synthesized by the reactions of (NH4)2MS4 ((NH4)2MOS3) (M = Mo, W), AgSCN with 1,2-(PPh2)2-1,2-C2B10H10 (L) in dichloromethane and characterized by elemental analysis, FT-IR, UV–Vis, 1H and 13C NMR spectroscopy and X-ray structure determination. For the first time, the W–Ag–S cluster has been proved to show luminescence property induced by ligand to ligand charge transfer (LLCT) in CH2Cl2 solution at room temperature.

Three dinuclear copper(I) complexes with the formula [Cu2(μ-X)2(1,2-(PiPr2)2-1,2-C2B10H10)2] (X = Cl (1), Br (2), I (3)) containing the closo carborane diphosphine ligand 1,2-(PiPr2)2-1,2-C2B10H10 have been prepared and characterized by elemental analysis, FT-IR and X-ray structure determination. The X-ray structure analyses revealed that the three complexes were isostructural and crystallized in the monoclinic system and space group C2/m. The carborane cage ligand was coordinated bidentately to the Cu(I) center through its two phosphorus atoms, and the coordination geometry around each copper atom was distorted tetrahedral. Two halogen atoms bridged the metal centers forming a dimer structure [Cu2(μ-X)2(1,2-(PiPr2)2-1,2-C2B10H10)2], which were linked into 2D supramolecular networks through novel C–H⋯H–B dihydrogen bonding interactions.

An unusual solvent effect on the synthesis of five manganese complexes [Mn2(L1)2(Py)4](1), [Mn2(L1)2(DMSO)4](2), [Mn4(L2)4(OH)4](3), [Mn4(L3)2(DMSO)7(H2O)](4), and [Mn6O2(L4)4(OAc)2(OMe)2(DMSO)4]·MeOH] (5), (H3L1 = 5-(2-oxyphenyl)-pyrazole-3-carboxylic acid; H2L2 = 5-(2-oxyphenyl)-pyrazole-3-carboxylic acid amide; H4L3 = di-[5-(2-oxyphenyl)-pyrazole]-3-hydroxamic ether; and H2L4 = 5-(2-oxyphenyl)-pyrazole-3-carboxylic acid methyl ester) has been reported. Five complexes have been characterized by X-ray single crystal diffraction, IR, element analysis, thermogravimetric analysis and UV-vis spectra. The analysis reveals that complexes 1 and 2 are isostructural with a bimetallic six-membered ring and L1 from the decomposition of the original H4ppha (H4ppha = 5-(2-hydroxyphenyl)-pyrazole-3-hydroxamic acid) ligand. Complexes 3 and 4 are two tetranuclear clusters, and 3 possesses an aza12-metallacrown-4 core with L2 from the amide functionalization of the decomposition L1; while 4 represents a novel linear [Mn4N8O2] core with L3 from the condensation of L1 and H4ppha. Complex 5 is the first Mn6 cluster linked by two stacked, off-set 8-azametallacrown-3 subunits with [M–N–N–M–N–N–M–O] connectivity, and L4 derived from the esterification of L1. The magnetic behaviour of complexes 1–5 show the dominant antiferromagnetic interactions between metal centers, whereas complex 5 further reveals the coexistence of antiferromagnetic and ferromagnetic interactions, and slow magnetic relaxation at T < 6 K with S = 4 ground state, as well as field induced magnetization saturation.

Reaction of Mn(OAc)2·4H2O with the H2L ligand affords a new manganese 22-MC-8 azametallacrown [Mn8(μ3-O)2(μ3-OH)2(μ2-OH)2(L)6(OAc)2(OH2)4]·2DMF (H2L = 3-(2-oxyphenyl)-5-(pyrazin-2-yl)-1,2,4-triazole). The structural analysis of the complex reveals that the azaMC ring possesses –[Mn–O–Mn–N–N–Mn–N–N–Mn–N–N]– connectivity. The magnetic behavior of the complex shows the dominant antiferromagnetic interactions between the manganese ions with S = 4 and the frequency-dependent out-of-phase signal.

Two cobalt(II) compounds, namely, {[Co(HL)(bpy)(H2O)2]·DMF}n (1), and {[Co(HL)(bpe)]·0.5bpe}n (2) (H3L = 1,3-bis(2-carboxylphenoxy)benzoic acid, bpy = 4,4′-bipyridine, bpe = 4,4′-vinylenedipyridine), have been synthesized using cobalt(II) transition metal salt with phenolic carboxylic acid and different N-donor ligands. The compounds were fully characterized by elemental analysis, infrared spectroscopy (IR), single crystal X-ray diffraction analysis, and thermogravimetric analysis (TGA). Both compounds exhibit 2-D (4,4)-sql networks but with a wavelike and a double layered arrangement, respectively. Remarkably, these two compounds not only exhibit field-induced single-ion relaxation magnetization but also exceptional catalytic activities of benzylic C–H oxidation (conv. 90.3–99%; sele. 98.1–99%).