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ABSTRACT: Two hexanuclear Cu(I) clusters [Cu(I)(3)(4-ptt)(3)](2)·3DMF·3H(2)O (1) and [Cu(I)(4-ptt)](6)·8DMF·7H(2)O (2) (4-Hptt = 5-(pyridin-4-yl)-1H-1,2,4-triazole-3-thiol, DMF = N,N-dimethylformamide), were synthesized and characterized. Compounds 1 and 2 with similar coordination environments are isomers, but their detailed structures are different due to the reaction temperature tuning effect. Both 1 and 2 extend from monomers to 3D supramolecules with the help of hydrogen bonding between the triazole and pyridine from the 4-ptt ligands. The Cu(6)S(6) units of 1 pack in a polydirectional array, while the Cu(6)S(6) units in 2 extend in one direction and link the planes of adjacent ligands to enhance the delocalization of π electrons. Their varied Cu-Cu interactions and individual packing modes cause differences in luminescent and thermostable behaviors. Compound 1 exhibits an unusually long wavelength at about 900 nm and a higher thermal stability; while the emission of 2 splits into two bands (high-energy and low-energy emission bands) as the temperature decreases. Therefore, the emissions of 1 originate from a (3)CC transition, and those of 2 are from a mixture of (3)CC and MLCT.
Dalton Transactions 06/2012; 41(31):9411-6. · 3.84 Impact Factor
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ABSTRACT: Chlorine caged in! The chlorine-induced assembly of six shuttlecock-like tetranuclear Mn(II) building blocks generated in situ based on p-tert-butylthiacalix[4]arene and facial anions gave rise to a novel truncated distorted octahedral cationic coordination cage with a μ(5)-carbonato-bridged Mn(II)(24) core.
Chemistry 03/2012; 18(18):5536-40. · 5.93 Impact Factor
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ABSTRACT: A family of Mn(III)/Ni(II) heterometallic clusters, [Mn(III)(4)Ni(II)(5)(OH)(4)(hmcH)(4)(pao)(8)Cl(2)]·5DMF (1·5DMF), [Mn(III)(3)Ni(II)(6)(N(3))(2)(pao)(10)(hmcH)(2)(OH)(4)]Br·2MeOH·9H(2)O (2·2MeOH·9H(2)O), [Mn(III)Ni(II)(5)(N(3))(4)(pao)(6)(paoH)(2)(OH)(2)](ClO(4))·MeOH·3H(2)O (3·MeOH·3H(2)O), and [Mn(III)(2)Ni(II)(2)(hmcH)(2)(pao)(4)(OMe)(2)(MeOH)(2)]·2H(2)O·6MeOH (4·2H(2)O·6MeOH) [paoH = pyridine-2-aldoxime, hmcH(3) = 2, 6-Bis(hydroxymethyl)-p-cresol], has been prepared by reactions of Mn(II) salts with [Ni(paoH)(2)Cl(2)], hmcH(3), and NEt(3) in the presence or absence of NaN(3) and characterized. Complex 1 has a Mn(III)(4)Ni(II)(5) topology which can be described as two corner-sharing [Mn(2)Ni(2)O(2)] butterfly units bridged to an outer Mn atom and a Ni atom through alkoxide groups. Complex 2 has a Mn(III)(3)Ni(II)(6) topology that is similar to that of 1 but with two corner-sharing [Mn(2)Ni(2)O(2)] units of 1 replaced with [Mn(3)NiO(2)] and [MnNi(3)O(2)] units as well as the outer Mn atom of 1 substituted by a Ni atom. 1 and 2 represent the largest 3d heterometal/oxime clusters and the biggest Mn(III)Ni(II) clusters discovered to date. Complex 3 possesses a [MnNi(5)(μ-N(3))(2)(μ-OH)(2)](9+) core, whose topology is observed for the first time in a discrete molecule. Careful examination of the structures of 1-3 indicates that the Mn/Ni ratios of the complexes are likely associated with the presence of the different coligands hmcH(2-) and/or N(3)(-). Complex 4 has a Mn(III)(2)Ni(II)(2) defective double-cubane topology. Variable-temperature, solid-state dc and ac magnetization studies were carried out on complexes 1-4. Fitting of the obtained M/(Nμ(B)) vs H/T data gave S = 5, g = 1.94, and D = -0.38 cm(-1) for 1 and S = 3, g = 2.05, and D = -0.86 cm(-1) for 3. The ground state for 2 was determined from ac data, which indicated an S = 5 ground state. For 4, the pairwise exchange interactions were determined by fitting the susceptibility data vs T based on a 3-J model. Complex 1 exhibits out-of-phase ac susceptibility signals, indicating it may be a SMM.
Inorganic Chemistry 09/2011; 50(20):10342-52. · 4.60 Impact Factor
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ABSTRACT: The use of phosphonic acids in the synthesis of mixed-metal CeMn complexes has led to the formation of two phosphonate complexes with unusual topologies: [Ce(2)Mn(6)O(6)(OH)(5)(t-BuPO(3))(6)(O(2)CMe)(3)] x 53 H(2)O (1 x 53 H(2)O) and [Ce(22)Mn(12)O(34)(MePO(3))(12)(O(2)CMe)(33)(OMe)(6)(NO(3))(H(2)O)(12)](n) (2). The two mixed-metal CeMn complexes were both prepared from a reaction system containing Mn(O(2)CMe)(2) and (NH(4))(2)[Ce(NO(3))(6)] with similar procedures except for using different phosphonic acids (tert-butylphosphonic acid and methylphosphonic acid, respectively) as coligands. Both complexes possess rare topology of triangular type, with compound 1 being a 0D discrete cluster, whereas, compound 2 is a 1D polymer. The octanuclear core of complex 1 is composed of three symmetry equivalent distorted cubanes {Ce(IV)(2)Mn(IV)(2)O(2)(OH)(2)} sharing a trigonal-bipyramidal unit {Ce(IV)(2)(OH)(3)} in the centre. Compound 2 is a one-dimensional chain polymer of identical Ce(22)Mn(12)O(34) units linked together by NO(3)(-) and MeCO(2)(-) groups, while the Ce(22)Mn(12)O(34) unit is constituted by two centrosymmetric Ce(9)(IV)Ce(2)(III)Mn(IV)(6)O(17) subunits, which features three identical distorted cubanes {Ce(IV)(2)Mn(IV)(2)O(4)} connecting to a central trigonal-bipyramidal unit {Ce(IV)(3)O(2)}, and two additional Ce(III) ions capping the top and bottom of the central trigonal bipyramid by six MePO(3)(2-) ligands. Complexes 1 and 2 are the first high-nuclearity Mn/Ln aggregates reported to date using phosphonates as ligands. Magnetic susceptibility measurements reveal that compound 1 displays dominant ferromagnetic interactions between the adjacent metal ions with the best fit parameters for the exchanges are J(1) = 6.186 cm(-1), J(2) = 4.172 cm(-1), and with a result of S = 9 ground state confirmed by the M versus HT(-1) data, which indicates the spins of all the six Mn(IV) ions in the cluster are parallel to each other. In contrast, the data for 2 reveals overall antiferromagnetic couplings within the cluster and a resulting S = 6 ground state. Both the in-phase signal chi'(M)T and out-of-phase signal chi''(M) of the two complexes exhibit frequency-dependent below approximate 3 K.
Dalton Transactions 08/2010; 39(31):7276-85. · 3.84 Impact Factor
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Angewandte Chemie International Edition 10/2009; 48(39):7104. · 13.45 Impact Factor
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Angewandte Chemie International Edition 09/2009; 48(39):7176-9. · 13.45 Impact Factor
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ABSTRACT: A family of manganese complexes, [Mn 5O 3( t-BuPO 3) 2(MeCOO) 5(H 2O)(phen) 2] ( 1), [Mn 5O 3( t-BuPO 3) 2(PhCOO) 5(phen) 2] ( 2), [Mn 4O 2( t-BuPO 3) 2(RCOO) 4(bpy) 2] (R = Me, ( 3); R = Ph, ( 4)), NBu (n) 4[Mn 4O 2(EtCOO) 3(MeCOO) 4(pic) 2] ( 5), NR' 4[Mn 4O 2( i-PrCOO) 7(pic) 2] (R' = Bu (n) , ( 6); R' = Et, ( 7)), were synthesized and characterized. The seven manganese clusters were all prepared from a reaction system containing tert-butylphosphonic acid, Mn(O 2CR) 2 (R = Me, Ph) and NR' 4MnO 4 (R' = Bu (n) , Et) with similar procedures except for using different N-containing ligands (1,10-phenanthroline (phen), 2,2'-bipyridine (bpy) and picolinic acid (picH)) as coligands. The structures of these complexes vary with the N-containing donors. Both the cores of complexes 1 and 2 feature three mu 3-O and two capping t-BuPO 3 (2-) groups bridging five Mn (III) atoms to form a basket-like cage structure. Complexes 3 and 4 both have one [Mn 4(mu 3-O) 2] (8+) core with four coplanar Mn (III) atoms disposed in an extended "butterfly-like" arrangement and two capping mu 3- t-BuPO 3 (2-) binding to three manganese centers above and below the Mn 4 plane. Complexes 5, 6, and 7 all possess one [Mn 4(mu 3-O) 2] (8+) core just as complexes 3 and 4, but they display a folded "butterfly-like" conformation with the four Mn (III) atoms nonplanar. Thus, the seven compounds are classified into three types, and three representative compounds 1.2H 2O.MeOH.MeCN , 3.6H 2O.2MeCOOH , and 5.0.5H 2O have been characterized by IR spectroscopy, ESI-MS spectroscopy, magnetic measurements and in situ UV-vis-NIR spectroelectrochemical analysis. Magnetic susceptibility measurements reveal the existence of both ferromagnetic and antiferromagnetic interactions between the adjacent Mn (III) ions in compound 1.2H 2O.MeOH.MeCN , and antiferromagnetic interactions in 3.6H 2O.2MeCOOH and 5.0.5H 2O. Fitting the experimental data led to the following parameters: J 1 = -2.18 cm (-1), J 2 = 6.93 cm (-1), J 3 = -13.94 cm (-1), J 4 = -9.62 cm (-1), J 5 = -11.17 cm (-1), g = 2.00 ( 1.2H 2O.MeOH.MeCN ), J 1 = -5.41 cm (-1), J 2 = -35.44 cm (-1), g = 2.13, zJ' = -1.55 cm (-1) ( 3.6H 2O.2MeCOOH ) and J 1 = -2.29 cm (-1), J 2 = -35.21 cm (-1), g = 2.02, zJ' = -0.86 cm (-1) ( 5.0.5H 2O ).
Inorganic Chemistry 08/2008; 47(13):5580-90. · 4.60 Impact Factor
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CrystEngComm 01/2008; 10(7). · 3.84 Impact Factor
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ABSTRACT: A novel three-dimensional (3D) microporous lanthanide−organic framework [Nd(2,5-pydc)(Ac)(H2O)]n·2nH2O (1) has been prepared under hydrothermal conditions. The results of an X-ray crystallographic analysis revealed that compound 1 has a 3D nanotubular structure. From the topological point of view, the intricate 3D framework of compound 1 can be specified by the Schläfli symbol (42638) as a zeolite ABW net. The H2 adsorption isotherm at 77 K shows an uptake of 132 cm3 g−1 at 1.0 atm.
12/2007;
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You-Gui Huang, Da-Qiang Yuan,
Long Pan,
Fei-Long Jiang,
Ming-Yan Wu,
Xu-Dong Zhang,
Wei Wei,
Qiang Gao,
Jeong Yong Lee,
Jing Li,
Mao-Chun Hong
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ABSTRACT: Two 3D cobalt-organic frameworks formulated as [Co3(2,4-pydc)2(micro3-OH)2]n.5nH2O (1) and [Co3(2,4-pydc)2(micro3-OH)2(H2O)]n.7nH2O (2) (2,4-pydc=pyridine-2,4-dicarboxylate) have been hydrothermally synthesized and characterized. Both compounds 1 and 2 exhibit the 3D porous frameworks with hydroxyl-bridged metal Delta-chains. However, in comparison with only two crystallographically independent CoII ions in a unit of 2, three crystallographically independent CoII ions are found in an asymmetric unit of 1, where their Delta-chains are constructed by two types of vertexes sharing quadrangles formed via edge-sharing triangles. Magnetic studies show that 1 exhibits spin-canted antiferomagnetism and a field-induced spin-flop transition while 2 behaves as a normal antiferromagnet. The magnetic properties are largely retained by the porous frameworks of dehydrated 1 and 2 compounds. Gas adsorption measurements indicate that both the dehydrated compounds absorb H2 into their pores.
Inorganic Chemistry 12/2007; 46(23):9609-15. · 4.60 Impact Factor
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ABSTRACT: Two 3D cobalt−organic frameworks formulated as [Co3(2,4-pydc)2(μ3-OH)2]n·5nH2O (1) and [Co3(2,4-pydc)2(μ3-OH)2(H2O)]n·7nH2O (2) (2,4-pydc = pyridine-2,4-dicarboxylate) have been hydrothermally synthesized and characterized. Both compounds 1 and 2 exhibit the 3D porous frameworks with hydroxyl-bridged metal Δ-chains. However, in comparison with only two crystallographically independent CoII ions in a unit of 2, three crystallographically independent CoII ions are found in an asymmetric unit of 1, where their Δ-chains are constructed by two types of vertexes sharing quadrangles formed via edge-sharing triangles. Magnetic studies show that 1 exhibits spin-canted antiferomagnetism and a field-induced spin-flop transition while 2 behaves as a normal antiferromagnet. The magnetic properties are largely retained by the porous frameworks of dehydrated 1 and 2 compounds. Gas adsorption measurements indicate that both the dehydrated compounds absorb H2 into their pores.
10/2007;
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Supramolecular Chemistry 09/2007; 19(6):411-417. · 2.14 Impact Factor
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ABSTRACT: A porous anionic framework with cubic symmetry and multi-intersecting open channels, {[H2tmdp]3[In6(btc)8]·40H2O}n (1) (tmdp= 4,4‘-trimethylene dipiperidine, H3btc=1,3,5-benzenetricarboxylic acid), is reported. Complex 1 crystallizes in the cubic space group I4̄3d (a = b = c = 20.3732(8) Å, V = 8456.2(6) Å3, and Z = 2). Its cagelike units, In9(btc)11, constitute a large accessible void with 65.4% of the total volume. The cationic guests located in the channels can be exchanged with inorganic ions, such as K+, NH4+, Ca2+, Sr2+, and Ba2+.
07/2007;
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ABSTRACT: A novel three-dimensional water network containing both coordinated and lattice water molecules was obtained in the compound [Co2(BPTC)(H2O)6]n·11nH2O (1). The water network was formed by the hierarchic assembly of bilayer water nanotubes of octamers with crisscross pentamers and helical water chains. A startling feature is the large (H2O)36 water crowns in the water layer in the [001] plane. Leaving the water molecules from the coordination spheres out of consideration, the water network is a two-dimensional water layer formed by T5(2)5(3) water tapes.
07/2007;
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ABSTRACT: A novel sandwich-type polyoxometalate incorporating a unique hybrid hexanuclear copper cluster, [Cu(enMe)2]2{[Cu(enMe)2(H2O)]2[Cu6(enMe)2(B-a-SiW9O34)2]}.4H2O (1, enMe=1,2-diaminopropane), has been hydrothermally synthesized and structurally characterized by the elemental analyses, IR spectroscopy, TG analysis, magnetic properties, and single-crystal X-ray diffraction analysis. Crystal data for 1: triclinic, P; a=12.5105(2), b=14.3710(2), c=17.2687(2) A; alpha=98.834(1), beta=110.744(1), gamma=104.711(1) degrees; V=2704.57(7) A3; rho=3.646 g/cm3; Z=1. X-ray crystallographic study shows that the molecular structure of 1 contains 10 copper ions: Six of them form an unprecedented inorganic-organic hybrid Cu6 cluster via edge-sharing combination of two CuO6 octahedra, two CuO5, and two CuO3N2 square pyramids and are encapsulated between two {B-a-SiW9O34} units. Two of them form two [Cu(enMe)2(H2O)]2+ complexes and further attach to the two {B-a-SiW9O34} units via two Cu-O=W bridges, acting as a decorated role. The remaining two form isolated [Cu(enMe)2]2+ complexes playing roles of charge-compensation and space-fillers. Magnetization measurement reveals that the hexanuclear copper cluster exhibits overall ferromagnetic interactions.
Inorganic Chemistry 06/2007; 46(11):4569-74. · 4.60 Impact Factor
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ABSTRACT: The hydrothermal reactions of [A-alpha-SiW(9)O(34)](10-)/[A-alpha-PW(9)O(34)](9-) with NiCl(2) x 6H(2)O and amines yielded four unprecedented hybrid high-nuclear Ni-subsituted polyoxotungstates.
Chemical Communications 06/2007; · 6.17 Impact Factor
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ABSTRACT: A series of new lanthanide hybrids [Ln3(mu-OH)4 (2,5-pydc)(2,5-Hpydc)3(H2O)4]n (Ln = Gd (1), Dy (2), Er (3), Eu (4), Sm (5), Yb (6), Y (7); 2,5-pydc=pyridine-2,5-dicarboxylate), as clustered lanthanide oxide ring tunnels with helical dodecahedral chains and fully 3D Ln-O-Ln connectivity, has been hydrothermally synthesized and characterized. The inorganic skeleton of the hybrid can be specified by the Schläfli symbol (6210)2 (64102) as a single 3D (3,4)-connected net. The luminescence properties have been studied, and the results showed that the Dy(III) (2) and Eu(III) (4) complexes exhibited sensitized luminescence in the visible region. Variable-temperature magnetic susceptibility measurements of 1-6 showed that the complexes 1-3 are nearly paramagnets, whereas the depopulation of the Stark levels in complexes 4-6 leads to a continuous decrease in mu(eff) when the sample is cooled from 300 to 2 K.
Inorganic Chemistry 03/2007; 46(4):1171-6. · 4.60 Impact Factor
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Acta Crystallographica Section E-structure Reports Online - ACTA CRYSTALLOGR E-STRUCT REP. 01/2007; 63(3).
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ABSTRACT: Two novel high-symmetry 3D porous frameworks, [Cd5(tetrazolate)9(OH)(H2O)]n.5nH2O (1) and [Cd5(5-aminotetrazolate)9(NO3)]n.3nH2O (2), have been synthesized under hydrothermal conditions and characterized by single-crystal X-ray diffraction analysis. The structures of 1 and 2 are characteristic of hexagonal tunnels through the trigonal-prismatic and hexagonal tubelike building units and exhibit their high stabilities of porous frameworks against the removal of the guest molecules.
Inorganic Chemistry 08/2006; 45(15):5760-6. · 4.60 Impact Factor
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ABSTRACT: The self-assembly of d,l-amino acids and Cu(NO3)2·3H2O with 4,4‘-bipyridine in basic ethanol/aqueous solution gave rise to two distinct three-dimensional (3D) supramolecular architectures {[Cu2(d-ala)(l-ala)(4,4‘-bipy)2](NO3)2·5H2O}n (1) and {[Cu2(d-phe)(l-phe)(4,4‘-bipy)2](NO3)(OH)·5H2O}n (ala = alanine anion, phe = phenylalanine anion, 4,4‘-bipy = 4,4‘-bipyridine) (2). In 1, Cu(II) centers chelated by deprotoned d,l-alanine direct linear 4,4‘-bipy to form a one-dimensional (1D) helical chain, which is further assembled into 3D helical array through interchain hydrogen bonds and anion guest chains. In 2, Cu(II) centers chelated by deprotoned d,l-phenylalanine direct 4,4‘-bipy to form a 1D twisted coordination polymeric chain that interacts with four adjacent chains through complementary coordination interactions and two chains through weak π−π interactions to give a 3D porous framework.
02/2006;
