Co-reporter:Xia Li, Benlai Wu, Ruiying Wang, Hongyun Zhang, Caoyuan Niu, Yunyin Niu and Hongwei Hou
Inorganic Chemistry March 15, 2010 Volume 49(Issue 6) pp:2600-2613
Publication Date(Web):February 8, 2010
DOI:10.1021/ic901113p
Five interesting metal−organic nanostructures and networks, [Ni4(HL)4(bpy)(py)(H2O)5]2·0.5H2O (1), [Co4(HL)4(bpy)(py)(H2O)5]2·0.5H2O (2), [Ni4(HL)4(H2O)7]n·nH2O (3), [Ni4(HL)4(bpy)2(H2O)4]n (4), and [Cd4(HL)4(H2O)]n (5), were synthesized hydrothermally [H3L = 2-(pyridin-2-yl)-1H-imidazole-4,5-dicarboxylate acid, py = pyridine, and bpy = 4,4′-bipyridine]. Intriguingly, all compounds consist of novel metallacalix[4]arene building blocks M4(HL)4, where doubly deprotonated HL in the same bichelating fashion of μ-kN,N′:kO,N′′ displays a strong coordination orientation by cooperation of the 4,5-imidazoledicarboxylate and 2-pyridyl groups. Very interestingly, the symmetry of M4(HL)4 and the linkage styles between metal nodes and HL in M4(HL)4 are sensitive to the reaction conditions, and the resulting structural motifs vary with secondary ligands and metal nodes. In 1 and 2, two C1-symmetric M4(HL)4 units are bpy-bridged into dimeric chiral nanomolecules with two different cavities. As deprotonated with NaOH, the combination of NiII and HL forms a pseudo-S4- or S4-symmetric M4(HL)4, which further assembles into 1D chiral crystals 3 or rare 3D crystals 4 of bpy-bridged 5-fold interpenetrating diamondoid architecture with metallacalix[4]arene building blocks as novel 4-connecting nodes, and the combination of CdII and HL forms an 8-connected C2-symmetric M4(HL)4 that fabricates the α-Po net of 5. Notably, those large M4(HL)4 units are potentially highly connected building blocks in a hierarchical assembly of metal−organic networks. Magnetic studies disclose antiferromagnetic interactions in M4(HL)4 of 1−4. The magnetic data for 1, 3, and 4, all containing isomeric Ni4(HL)4 units, are analyzed by an equilateral quadrangle isotropic model combined with the molecular-field approximation with J = −4.00(2), −3.39(2), and −2.72(3) cm−1, respectively, presenting a stronger comparison between the structure and magnetism. The emission of 5 is odd, which perhaps is relative to the bichelating fashion of ligand HL and a rare coordination geometry of CdII. Moreover, the thermal stability and gas sorption properties of these compounds were measured.
Co-reporter:Ruiying Wang, Lina Liu, Lulu Lv, Xing Wang, Rui Chen, and Benlai Wu
Crystal Growth & Design July 5, 2017 Volume 17(Issue 7) pp:3616-3616
Publication Date(Web):May 19, 2017
DOI:10.1021/acs.cgd.6b01768
Five 1–3D cadmium(II) coordination polymers, namely, [Cd(HL)(DMF)]n (1), [Cd4(HL)4(H2O)6]n (2), [Cd(HL)(phen)]n (3), [Cd2(HL)2(bpy)]n (4), and {[Cd3(HL)3(pbim)2]·H2O}n (5), have been synthesized and fully characterized [H3L = 2-(5-bromo-pyridin-3-yl)-1H-imidazole-4,5-dicarboxylic acid, DMF = N,N-dimethylformamide, phen = 1,10-phenanthroline, bpy = 4,4′-bipyridine, and pbim = 1,1′-(5-methyl-1,3-phenylene)bis(1H-imidazole)]. In those complexes, the doubly deprotonated H3L ligands and CdII ions display versatile coordination modes to construct various structures with interesting topologies. Complex 1 is a 2D helical structure with (4·82) topology built up from 3-connected (HL)2– and CdII nodes. Complex 2 containing (HL)2–-bridged tetranuclear CdII subunits is a 3D helical structure where both (HL)2– and CdII adopt three coordination modes to form a rare 3-connected network with (5·8·12)2(5·12·16)2(5·82)(82·12) topology. Substituting the smaller terminal ligands DMF and water with the larger terminal ligand phen, (HL)2– ligands only use their imidazoledicarboxylate groups to bis-chelate CdII into a chain structure of 3. Complex 4 is a (3,4)-connected 3D network with (4·82)(4·82·103) topology built up from the (HL)2–-bridged (4,82) mesolayer observed in 1 being further linked by rodlike bpy bridges replacing terminal ligand DMF. Complex 5 consists of (HL)2–- and pbim-bridged macrocycle chains and is a (3,4)-connected 2D novel network with (3·4·8)2(3·4·5·82·9)2(32·82·92) topology. As expected, the strongly bis-chelating coordination mode μ-kN,O:kN′,O′ of the imidazoledicarboxylate of (HL)2– absolutely dominates the assemblies with CdII in those complexes. Intriguingly, the additional ligands, such as smaller terminal ligands water and DMF, larger planar terminal ligand phen, as well as rodlike and V-shaped bridges bpy and pbim, exert obvious influence on the coordination modes of ligands (HL)2– and the resulting architectures. Clearly, larger terminal and bridging ligands phen and pbim could limit the coordination of the pyridyl of (HL)2– through steric hindrance. Meanwhile, the solid-state photoluminescence of those compounds at room temperature was also investigated, and the results indicate that their emissions are significantly influenced by the additional ligands incorporating into the networks.
Co-reporter:Lu-Lu Lv, Li-Jun Zhang, Hong Zhao, Ben-Lai Wu
Polyhedron 2016 115() pp: 204-211
Publication Date(Web):5 September 2016
DOI:10.1016/j.poly.2016.05.019
Using V-shaped mixed ligands bis-imidazole and aromatic carboxylic acids, five new coordination polymers namely, {[Ni(B-im)(Br-a)Cl]·H2O}n (1), {[Ni(B-im)(I-a)(H2O)2]·0.5H2O}n (2), [Ni(B-im)(I-a)(H2O)2]n (3), [Ni(B-im)(M-a)(H2O)2]n (4) and {[Mn2(B-im)2(I-a)2]·2H2O}n (5) [B-im = 1,1′-(5-methyl-1,3-phenylene)bis(1H-imidazole), Br-a = 5-bromonicotinic acid, I-a = isophthalic acid and M-a = 5-methylisophthalic acid] were solvothermally synthesized and fully characterized by IR spectra, element analyses, X-ray powder and single-crystal diffractions, and thermogravimetric analyses. Complexes 1 and 2 feature polymeric macrocyclic chain structures containing interesting nanotubular channels, which are constructed by bridging 30-membered macrocyclic [Ni3(B-im)3] subunits with Br-a ligands and by bridging folded 20-membered macrocyclic [Ni2(B-im)2] subunits with I-a ligands, respectively. Isomorphic complexes 3 and 4 represent double-chain structures containing folded 18-membered macrocyclic [Ni2(B-im)(I-a)] subunits and [Ni2(B-im)(M-a)] subunits, respectively. Complex 5 is a 2D porous coordination polymer containing novel chiral four-stranded Mn(II) chains consisting of two (B-im)-bridged aspiral chiral chains and two (I-a)-bridged heterochiral coaxial 21-helical chains. The results of thermal gravimetric analyses suggest that the dehydrated frameworks of 1–5 are stable up to 320 °C. Additionally, the magnetism of complexes 3 and 5 were also investigated.A serial of Ni(II) and Mn(II) coordination polymers based on V-shaped mixed ligands bis-imidazole and aromatic carboxylic acids were solvothermally synthesized and fully characterized. Intriguingly, sorted-recognition and hierarchical assembly between Ni(II) and mixed ligands result in novel nanotubes.
Co-reporter:Li-Na Liu, Si-Wen Zhang, Ya-Dong Wang, Xiao-Gang Guo, Lian Wu, Ben-Lai Wu
Inorganica Chimica Acta 2014 Volume 423(Part A) pp:176-183
Publication Date(Web):1 November 2014
DOI:10.1016/j.ica.2014.08.010
Co-reporter:Wen-Juan Ma, Zhi-Yang Gao, Shu Zhu, Ben-Lai Wu
Polyhedron 2014 Volume 73() pp:59-66
Publication Date(Web):8 May 2014
DOI:10.1016/j.poly.2014.02.021
Tetranuclear square grids, namely, [Cd4(L–O)4]·1.5DMF (1), [Ni4(L–O)4]·H2O (2), [Zn4(L–O)4]·3H2O (3), [Zn4(L–O)4] (4), [Cu4(L–O)4]·H2O (5), and {[Cu4(L–O)4][Cu4(L–O)4]}·2.5DMF·1.5H2O (6) (DMF = N,N-dimethylformamide, H2L–O = 2,6-bis(pyrazine-2-carboxamido)pyridine-N-oxide), formed by the reactions of M ions (M = CdII, NiII, ZnII and CuII) with pyridyldicarboxamide ligands 2,6-bis(pyrazine-2-carboxamido)pyridine (H2L), was fully characterized. Notably, the central pyridines of ligands H2L were oxidized into pyridine-N-oxides under air conditions, producing the new anionic ligands (L–O)2− to fabricate those grids. In those square grids every octahedrally coordinated metal node is chelated by two doubly deprotonated ligands (L–O)2− in the mer configuration, and each ligand (L–O)2− acts as a rigid bis(tridentate) linker with the Ncarboxamide and one Npyrazine in each arm chelating metal ions plus the O atom in the pyridine-N-oxide group bridging the two bound M ions. The CdII and ZnII grids show uncommonly-excellent thermal stabilities and interesting green emissions. Magnetic studies upon grid [Ni4(L–O)4] suggest an antiferromagnetic coupling between the adjacent NiII mainly exchanged through μ–O with a coupling constant of J = −15.06 cm−1.Graphical abstractA series of functionalized square [2 × 2] grids [M4(L–O)4] was prepared by the reactions of metal ions M with ligands 2,6-bis(pyrazine-2-carboxamido)pyridine (H2L) whose central pyridine were interestingly oxidized into pyridine-N-oxide in the formation of those grids to produce the new anionic ligands (L–O)2−. The selective oxidation of the central pyridine of H2L into pyridine-N-oxide through in situ reactions under an air condition as well as the properties of the resultant grids is of a certain practical significance.
Co-reporter:Benlai Wu, Song Wang, Ruiying Wang, Jinxia Xu, Daqiang Yuan, and Hongwei Hou
Crystal Growth & Design 2013 Volume 13(Issue 2) pp:518-525
Publication Date(Web):December 18, 2012
DOI:10.1021/cg300971r
An intentionally synthesized chiral terpyridyl ligand S-2(4-(2,6-di(pyridin-2-yl)pyridin-4-yl)-benzylamino)propanoic acid (H2L) was used to construct two chiral NiII complexes, [Ni2(HL)2(N3)(H2O)](N3)·19H2O (1) and [Ni2(HL)2(N3)2]·7H2O (2). Both complexes are dinuclear metallocyclic complexes. The monoanionic form (HL)− of the chiral ligand coordinates to the metal centers in a bichelating antiparallel fashion to form the metallomacrocycles where the chiral metallocycles Ni2(HL)2 template the formation of a novel chiral 3D zeolite-like water framework with nanometer cages trapping the metallocycles or anchor chiral water chains in the 1D channels of a resulting chiral 3D supermolecule, respectively.
Co-reporter:Yameng Li, Zhanfeng Ju, Benlai Wu, and Daqiang Yuan
Crystal Growth & Design 2013 Volume 13(Issue 9) pp:4125-4130
Publication Date(Web):July 29, 2013
DOI:10.1021/cg400948e
A 2-fold interpenetrated microporous MOF [Ni2(C2O4)(L)2]n·6nH2O (HL = 4,2′:4″,2′-terpyridine-4′-carboxylic acid) (1) was synthesized and structurally characterized. 1 has obvious 1D channels along the crystallographic a and c axes with a pore size of 5.7 to 6.9 Å. Topological analysis shows that the framework of 1 can be interpreted as a (3,4)-connected net with point symbol (63)(65·8). 1 exhibits high water and thermal stability, which is demonstrated by TGA, PXRD, and VT-PXRD. Additionally, the high temperature structure of 1′ (433 K) undoubtedly demonstrates the stability of the framework. More importantly, 1 shows high selectivities for CO2 over N2, H2, and CH4 at low pressure and 273 K.
Co-reporter:Xiaoju Yuan, Xiaoxia Zhang, Hong Zhao, Lina Liu, and Benlai Wu
Crystal Growth & Design 2013 Volume 13(Issue 11) pp:4859-4867
Publication Date(Web):September 17, 2013
DOI:10.1021/cg401022z
An acetate-functionalized purine-containing ligand, 2-(6-oxo-6,9-dihydro-1H-purin-1-yl) acetic acid (H2L), and its six new one–three-dimensional (1–3D) coordination polymers, [La(HL)2(NO3)(H2O)2]n (1), [Ce(HL)2(NO3)(H2O)2]n (2), [Pb(HL)2(H2O)2]n (3), [Cd(HL)2(H2O)2]n (4), [Cd(L)]n (5), and [Zn(L)]n (6), were synthesized and characterized. Single-crystal X-ray diffraction analyses reveal that the architectures of complexes 1–6 are built from the metal–organic helixes of ligands H2L. The overall structures range from the double helical chains of 1 and 2, and the 2D helical networks of 3 and 4, to the 3D coordination polymers of 5 and 6, containing 2D homochiral layers based on 1D metal–organic helixes. In those meso compounds, ligands H2L display differently anionic states, bridge modes, and especially unsymmetrical configurations with the sharp distortion between the acetate and purin in favor of constructing helical assemblies as expected. The plentiful hydrogen-bonding sites and π···π interactions originating from the bioactive purin group of ligand H2L greatly contribute to the formation of helical structures and the structural dimension, showing an intriguing ability in the supramolecular assembly. At room temperature, complexes 1–6 exhibit solid-state photoluminescences, with their emission wavelengths and intensities varying according to the central metal ions and the coordination patterns of ligand H2L. Additionally, the thermostabilities of these new complexes have been discussed in detail. In particular, 3D polymers 5 and 6 have extra high thermostabilities and stronger blue emissions, indicating potential applications in photoluminescent materials.
Co-reporter:Jinxia Xu;Ruiying Wang;Yameng Li;Zhiyang Gao;Rui Yao;Song Wang
European Journal of Inorganic Chemistry 2012 Volume 2012( Issue 20) pp:3349-3360
Publication Date(Web):
DOI:10.1002/ejic.201200100
Abstract
Four purely chiral supramolecular frameworks were constructed from a new chiral terpyridyl ligand, (S)-2{4-[2,6-bis(pyridin-2-yl)pyridin-4-yl]benzylamino}propanoic acid (H2ptpy). The resulting compounds 1–4, namely [Cd2(Hptpy)2(Ac)2]·3CH3OH·H2O (1) [Ni2(Hptpy)2(CH3OH)(H2O)](ClO4)2·CH3OH·H2O (2), [Ni2(Hptpy)2(H2O)2](SCN)2 (3), and [Cu2(Hptpy)2](dca)2·4H2O (4) (Ac = acetate and dca = dicyanamide) all consist of those chiral metallocyclic units. As expected, those chiral nanometallocycles not only induced a chiral array or helicates but also amplified chirality through hydrogen-bonding interactions, and finally aggregated into complicated higher-dimensional chiral supramolecular architectures with chiral voids for further use. The formation of the metallocyclic units is easily monitored by UV/Vis spectra. Spectrophotometric titrations were performed by titrating Na(Hptpy) with a soltution of Cd(Ac)2 in methanol, and the global stability constants of [Cd2(Hptpy)2]2+ (log β = 17.60) were calculated. In combination with the structural analyses and UV/Vis and ES mass spectra, it is tentatively deduced that metallocycle units in 1–4 are the thermodynamically favored species in solution. Both the chiral H2ptpy ligand and 1 in the solid state and in solution display purple emission. The bathochromic shift of 1 is mainly due to the bichelation and intrametallocyclic π–π interactions.
Co-reporter:Xiao-Ju Yuan, Rui-Ying Wang, Chun-Bo Mao, Lian Wu, Cai-Qing Chu, Rui Yao, Zhi-Yang Gao, Ben-Lai Wu, Hong-Yun Zhang
Inorganic Chemistry Communications 2012 Volume 15() pp:29-32
Publication Date(Web):January 2012
DOI:10.1016/j.inoche.2011.09.031
Schiff base complex [Co(L)2](ClO4)·(C3H6O)·(H2O) (1) was synthesized and structurally determined [L = 2-((E)-(3-aminopyridin-4-ylimino)methyl)-phenol and C3H6O = acetone]. With 1 as the ionophore a new Pb(II)-selective membrane electrode was exploited. The electrode exhibits Nernstian response to Pb(II) over a wide concentration range (1.0 × 10− 5 to 1.0 × 10− 2 M), with a slope of 23.9 mV/dec, a fast response time (t95% = 10 s), and a lower detection limit of 4.6 × 10− 6 M. It has acceptable selectivity for Pb(II) over a wide variety of other metal ions in a wide pH range of 4–13, showing practical detection for Pb(II).A new Pb(II)-selective membrane electrode with mononuclear Schiff base complex [Co(L)2](ClO4)·(C3H6O)·(H2O) (1) [L = 2-((E)-(3-aminopyridin-4-ylimino)methyl)-phenol and C3H6O = acetone] as the ionophore was synthesized and investigated.Highlights► Ionophore of Schiff base complex. ► Crystal structure of mononuclear Co(II) complex. ► Pb(II)-selective membrane electrode. ► Potentiometric sensor.
Co-reporter:Ya-Meng Li, Ben-Lai Wu, Da-Qiang Yuan
Inorganic Chemistry Communications 2012 Volume 22() pp:120-122
Publication Date(Web):August 2012
DOI:10.1016/j.inoche.2012.05.038
Two isostructural lanthanide complexes, [Ln2(INO)4(NO3)2]n·2nDMF [Ln = Eu (1), Tb (2)] (INO = isonicotinate-N-oxide; DMF = N,N-dimethylformamide), have been synthesized under the solvothermal condition and characterized by single-crystal X-ray diffraction, X-ray powder diffraction (XRD), thermogravimetric analysis (TGA) and elemental analysis (EA). In these two complexes, each dinuclear Ln(III) unit is connected with six neighboring dinuclear units, which finally constructs a three-dimensional (3D) framework. Along the crystallographic [0 0 1] direction, there are one-dimensional (1D) tunnels, in which free DMF molecules reside as guests. Additionally, the photoluminescent properties of 1 and 2 are also discussed.Two isostructural lanthanide(III) complexes both exhibit 3D microporous pcu structures containing di-nuclear lanthanide(III) units, in which free DMF molecules reside as guests. To further investigate the properties of the above complexes, the photoluminescent properties of 1 and 2 are also discussed.Highlights► Two microporous lanthanide(III) complexes both exhibit 3D pcu structures. ► Free DMF molecules reside in 1D tunnels as guests. ► The title complexes emit intensely in the visible region.
Co-reporter:Rui Yao, Yan Zhou, Lu-Yan Meng, Zhi-Yang Gao, Ben-Lai Wu, Hong-Yun Zhang
Inorganic Chemistry Communications 2012 Volume 24() pp:55-58
Publication Date(Web):October 2012
DOI:10.1016/j.inoche.2012.07.039
Reaction of U‐shaped flexible bis(amidopyridine) ligand L with CoCl2·6H2O in DMF produced a 2D coordination polymer [Co(L)2Cl2]n·4nDMF (1) with 1D channels guesting DMF molecules [L = N,N′-bis((pyridin-3-yl)methyl)pyridine-2,6-dicarboxamide, DMF = N,N′-dimethylformamide]. Complex 1 has corrugated flexible grid-like layers of a (4,4)-connected topology which consists of left- and right-handed helical chains sharing the common Co atoms. Investigation on the thermal stability and porosity shows that the porous network of 1 is rather stable up to 300 °C and has obvious adsorption for N2.A novel 2D porous coordination polymer with intriguing 1D nano-sized channels through the straight packing of corrugated flexible layers formed by left- and right-handed helical chains sharing the common Co atoms has been synthesized and characterized.Highlights► A novel 2D porous polymer with 1D nano-sized channels are synthesized. ► The title complex has corrugated flexible grid-like layers consisting of left- and right-handed helical chains. ► The title complex is rather stable up to 300 °C and has obvious adsorption for N2.
Co-reporter:Rui-Ying Wang, Lian Wu, Ya-Hui Yu, Xiao-Xia Zhang, Ben-Lai Wu, Hong-Yun Zhang
Polyhedron 2012 Volume 45(Issue 1) pp:170-176
Publication Date(Web):19 September 2012
DOI:10.1016/j.poly.2012.07.038
Through natural evaporation of the reaction solutions of ZnX2 (X = Cl−, CH3COO− and SCN−) and the ligand 2,6-bis(pyridine-4-carboxamido)pyridine (L), three new coordination compounds, [Zn(L)(Cl)2]n·nCH3OH·nH2O (1), [Zn(L)(CH3COO)2]2 (2) and [Zn(L)3(SCN)2]n (3) have been obtained. In these zinc(II) complexes, ligand L displays various conformers and coordination modes to fabricate the helical chain of 1, the discrete dimer of 2 and the zigzag chain of 3, with the coordination number of ZnII varying from 4 for 1, 5 for 2 to 6 for 3. Through complementary amide hydrogen bonds, their structures are extended into chiral layers, 1D ribbons and a 3D supramolecular network, respectively. Interestingly, the coordination numbers of ZnII, as well as the molecular and supramolecular structures of the resulting coordination complexes, are obviously tuned with the X anion used. Additionally, the TGA of 1 and 2 as well as the fluorescence of the free ligand L and 1 were measured in the solid state.Through natural evaporation of the reaction solutions of ZnX2 (X = Cl−, CH3COO− and SCN−) and the ligand 2,6-bis(pyridine-4-carboxamido)pyridine (L), three new zinc(II) complexes with different structures of helical chain, discrete dimer and zigzag chain were obtained. Interestingly, the coordination numbers of ZnII as well as the molecular and supramolecular structures of the resulting coordination complexes are obviously tuned with the X anion used.
Co-reporter:Ben-Lai Wu, Rui-Ying Wang, Hong-Yun Zhang, Hong-Wei Hou
Inorganica Chimica Acta 2011 Volume 375(Issue 1) pp:2-10
Publication Date(Web):1 September 2011
DOI:10.1016/j.ica.2011.05.029
Six new 1–3D coordination polymers of an unsymmetrical angular ligand 3-pyridin-4-ylbenzoate (L), namely, [Ni(L)2(C2H6O2)]n (1), [Cd(L)2(H2O)2]n·4H2O (2), [Zn2(OH)(L)3]n (3), [Fe2(OH)(L)3]n (4), [Ni(L)2(H2O)]n (5) and [Cd(L)2(H2O)]n (6) were hydro(solvo)thermally synthesized. They have abounding structure chemistry ranging from one-dimensional ribbons (1 and 2), and two-dimensional novel helical double-layered frameworks (3 and 4) to three-dimensional CdSO4-topological porous interpenetrating architectures with hydrophilic and hydrophobic channels regularly arraying (5 and 6). The labile conformations and coordination modes of ligand L, which were finely tuned by reaction conditions, perhaps play the key role in the construction of various architectures. Very interestingly, the slight difference in solvent system or temperature resulted in the distinct architectures of nickel(II) complexes 1 and 5 or cadmium(II) complexes 2 and 6. As expected, the unsymmetrical ligand L has a trend to construct metal-organic helixes as observed in 3 and 4. Thermogravimetric analysis of 5 shows the main framework retains stability until a higher temperature 379 °C. The 3D microporous network of 5 can slightly absorb for N2 and Ar. Compounds 2, 3 and 6 emit ligand-centered photoluminescence but with obviously different intensities owing to the structural diversities and coordinating water molecules.Graphical abstractSix new coordination polymers of an unsymmetrical angular ligand 3-pyridin-4-ylbenzoate were hydro(solvo)thermally synthesized. Their structures range from 1D ribbons, and 2D helical double-layered frameworks to 3D interpenetrating CdSO4-topological architectures, where the labile conformations and coordination modes of ligand L finely tuned by reaction conditions perhaps play the key role in the construction of various architectures.Highlights► Hydro(solvo)thermal syntheses of coordination polymers of 3-pyridin-4-ylbenzoic acid. ► Metal-organic frameworks tuned by ligand conformations. ► Novel metal-organic helical structures resulted from unsymmetrical angular ligand.
Co-reporter:Ben-Lai Wu, Rui-Ying Wang, E. Ye, Hong-Yun Zhang, Hong-Wei Hou
Inorganic Chemistry Communications 2010 Volume 13(Issue 1) pp:157-159
Publication Date(Web):January 2010
DOI:10.1016/j.inoche.2009.10.040
Co-reporter:Cao-Yuan Niu, Ben-Lai Wu, Xian-Fu Zheng, Xin-Sheng Wan, Hong-Yun Zhang, Yun-Yin Niu and Lu-Yan Meng
CrystEngComm 2009 vol. 11(Issue 7) pp:1373-1382
Publication Date(Web):19 Mar 2009
DOI:10.1039/B818745B
Reactions of one asymmetric ligand 1,6-dihydro-2-methyl-6-oxo-(3,4′-bipyridine)-5-carbonitrile (L1) with AgX (X = NO3−, BF4−, AsF6−, SbF6−) afforded two 1-D interpenetrating coordination polymers {[Ag2(L1)3]2·(CH3OH)3·(AsF6)4}n (1) and {[Ag2(L1)3]2·(SbF6)4}n (2), and two monomers [Ag(L1)2]·(NO3) (3) and [Ag(L1)2]·(CH3OH) (BF4) (4). The structural similarity between compounds 1 and 2, and the structural difference between compounds 1 and 2 and compounds 3 and 4 give evidences that the sizes of counteranions with the same polyhedron sometimes can not affect the supramolecular structures, but the polyhedra of counteranions sometimes can. The self-assembly of one angular ligand 1,3,4-thiadiazole-2,5-di-2-pyridyl (L2) with AgX (X = BF4−, ClO4−, PF6−, AsF6−, NO3−, SbF6−) produced five di-nuclear and one mono-nuclear silver(I) coordination compounds. In the three dinuclear compounds [Ag2(L2)2](BF4)2 (5), [Ag2(L2)2](ClO4)2 (6), and [Ag2(L2)2](PF6)2 (7), there are medium Ag–Ag interactions between two adjacent dimers, leading to a 1-D supramolecular chain. In the other two dimers [Ag2(L2)2](AsF6)2 (8) and [Ag2(L2)2](NO3)2(CH3OH) (9), however, no Ag–Ag interactions were found. When changing counteranion to the very large one SbF6−, the silver complex of L2 is a monomer [Ag(L2)2](SbF6) (10). The supramolecular structural diversity of compounds 7, 8, and 10, resulting from the volume changes of the octahedral counteranions shows that the sizes of counteranions with the same polyhedron can sometimes affect the supramolecular structures.
Co-reporter:Xia Li, Ben-Lai Wu, Cao-Yuan Niu, Yun-Yin Niu and Hong-Yun Zhang
Crystal Growth & Design 2009 Volume 9(Issue 8) pp:3423-3431
Publication Date(Web):June 17, 2009
DOI:10.1021/cg801321e
Six new metal−organic frameworks (MOFs), namely, {[Fe(HPIDC)(H2O)]·2H2O}n (1), [Cd(HPIDC)(H2O)]n (2), [Zn(HPIDC)(H2O)]n (3), {[Eu3(HPIDC)4(H2O)8]·NO3·4H2O}n (4), {[Tb3(HPIDC)4(H2O)8]·Cl·4H2O}n (5), and {[Y3(HPIDC)4(H2O)8]·Cl·4H2O}n (6), were hydrothermally synthesized and characterized (H3PIDC = 2-(pyridin-4-yl)-1H-imidazole-4,5-dicarboxylic acid). Single crystal X-ray diffractions show ligands H3PIDC are doubly deprotonated in all compounds, and the doubly deprotonated HPIDC2− coordinates in the μ3 or μ4 mode to generate 2D or 3D MOFs, displaying four coordination modes. Both 1 and 2 are 3D MOFs, but different in structure topologies. In 1 the ligand HPIDC2− and metal center Fe(II) act as 3-connected nodes to fabricate a (10,3) porous metal−organic net with 1D open channels where 1D zigzag water chains are reside through hydrogen-bonding interactions. This dehydrated porous material can absorb for N2, with a determined BET surface area of 9.07 m2 g−1. In 2, however, ligand HPIDC2− and metal center Cd(II) serve as 4-connected nodes to form a 3D honeycomb framework. Complexes 3−6 all are 2D MOFs built up from T-shaped 3-connected HPIDC2− and 3- or 4-connected metal nodes. With the 3-connected metal nodes Zn(II), a stairway-like MOF with (4.82) topology in 3 is created. As for 4-connected metal nodes Eu(III), Tb(III) or Y(III), isostructural MOFs with novel (42.6)2(4.62)2(42.63.8)2(42.62.82) nets in 4−6 form. Notably, ligands HPIDC2− in 1, 3 and 4−6 are all T-shaped 3-connectors, but belong to different coordination modes, and the coordination lability also results in structural diversity, even with similar 3-connected nodes such as Fe(II) in 1 and Zn(II) in 3. The luminescent nature for 4 and 5 is the typical narrow emission bands of Eu(III) and Tb(III) ions, respectively. For 2, 3 and 6, the slightly blue-shifted emission bands are mainly due to intraligand emissions.
Co-reporter:Ying-Xia Zhou;Xiao-Qing Shen;Chen-Xia Du;Ben-Lai Wu;Hong-Yun Zhang
European Journal of Inorganic Chemistry 2008 Volume 2008( Issue 27) pp:4280-4289
Publication Date(Web):
DOI:10.1002/ejic.200800434
Abstract
Reactions of TbCl3·6H2O with aromatic acids, namely, pyridine-2,3-dicarboxylic acid (H2pda), isophthalic acid (H2ipa) and isonicotinic acid (Hina) gave rise to three new coordination polymers {[Tb(pda)(Hpda)]·3H2O}n (1), {[KTb(ipa)2(H2O)3(μ-H2O)]·2H2O}n (2) and [Tb(ina)3(H2O)2]n (3), respectively. Complex 1 constructed by eight-coordinate TbIII nodes connected with completely and half-deprotonated pda and Hpda spacers is a novel 3D metal–organic architecture with nanosized hexagonal 1D channels hosting guest water, whereas complex 2 is a 2D heterometal sheet built by completely deprotonated ipa spacers bridging eight-coordinate KI and nine-coordinate TbIII. As for 3, deprotonated monoacid ina anions link eight-coordinate TbIII centres into a 1D double-chain structure. As excited at 320 nm, complexes 1–3 all display a serial of emissions centred at about 486, 545, 582 and 620 nm, which is assigned to the characteristic 5D4 7Fj (j = 6; 5; 4; 3) electronic transitions of TbIII. The overall fluorescence nature of 1–3 is extremely alike, but their fluorescence intensity and lifetime are affected by the architectures. Very interestingly, the fluorescence intensity of 2, especially emitting at 545 nm, is largely enhanced owing to the coordination of alkali metal KI in the TbIII–carboxylate network. Furthermore, thermal behaviours of 1–3 under a nitrogen atmosphere as well as the thermolysis nonisothermal kinetics of 2 are researched.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)
Co-reporter:Ben-Lai Wu, Ping Zhang, Yun-Yin Niu, Hong-yun Zhang, Zhong-Jun Li, Hong-Wei Hou
Inorganica Chimica Acta 2008 Volume 361(Issue 8) pp:2203-2209
Publication Date(Web):2 June 2008
DOI:10.1016/j.ica.2007.11.020
Self-assembly of 1,2-bis(3-pyridylcarboxylamide)benzene (H2bpb) with sulfate salts gave rise to three new coordination polymers, [Ni2(H2bpb)2(H2O)2(CH3OH)2(SO4)2]n · nCH3OH 1, [Co2(H2bpb)2(CH3OH)2(DMF)2(SO4)2]n · 0.5nH2O 2 (DMF = N,N′-dimethylformamide) and [Zn2(H2bpb)2(CH3OH)2(DMF)2(SO4)2]n · 0.5nH2O 3. They all crystallize in a monoclinic space group C2/c, with two crystallographically distinct metal nodes being surrounded by slightly distorted octahedra. There is a homologous chair-like unit with bridging ligand H2bpb as the back and bis(monodentate) sulfate anion as the seat in their crystal structures. Through the recognition of strong π⋯π stacking interactions between benzene rings, those chains formed by the unlimited extension of the chair-like units stack up to produce 1-D channels along c axis where lattice molecules and terminal ligands are accommodated. Interestingly, the trans,trans,syn achiral conformation with Cs symmetry of H2bpb which is further enforced by sulfate-bridged coordination and intramolecular hydrogen bonding in the chair-like units, controls over the assembling architectures. Further investigation on the thermal and fluorescent properties of complexes 1–3 shows that the homologous chair-like units in all complexes are stable enough until to 320 °C and that the fluorescence nature of H2bpb is not sensitive to its conformations.The reactions of 1,2-bis(3-pyridylcarboxylamide)benzene (H2bpb) with sulfate salts gave rise to three new complexes 1–3. All compounds are 1-D chain structures and have homologous chair-like units. Interestingly, the trans,trans,syn achiral conformation with Cs symmetry of H2bpb which is further enforced by sulfate-bridged coordination and intramolecular hydrogen bonding in chair-like units, may control over the assembling architectures.
Co-reporter:Xia Li ; Benlai Wu ; Ruiying Wang ; Hongyun Zhang ; Caoyuan Niu ; Yunyin Niu ;Hongwei Hou
Inorganic Chemistry () pp:
Publication Date(Web):February 8, 2010
DOI:10.1021/ic901113p
Five interesting metal−organic nanostructures and networks, [Ni4(HL)4(bpy)(py)(H2O)5]2·0.5H2O (1), [Co4(HL)4(bpy)(py)(H2O)5]2·0.5H2O (2), [Ni4(HL)4(H2O)7]n·nH2O (3), [Ni4(HL)4(bpy)2(H2O)4]n (4), and [Cd4(HL)4(H2O)]n (5), were synthesized hydrothermally [H3L = 2-(pyridin-2-yl)-1H-imidazole-4,5-dicarboxylate acid, py = pyridine, and bpy = 4,4′-bipyridine]. Intriguingly, all compounds consist of novel metallacalix[4]arene building blocks M4(HL)4, where doubly deprotonated HL in the same bichelating fashion of μ-kN,N′:kO,N′′ displays a strong coordination orientation by cooperation of the 4,5-imidazoledicarboxylate and 2-pyridyl groups. Very interestingly, the symmetry of M4(HL)4 and the linkage styles between metal nodes and HL in M4(HL)4 are sensitive to the reaction conditions, and the resulting structural motifs vary with secondary ligands and metal nodes. In 1 and 2, two C1-symmetric M4(HL)4 units are bpy-bridged into dimeric chiral nanomolecules with two different cavities. As deprotonated with NaOH, the combination of NiII and HL forms a pseudo-S4- or S4-symmetric M4(HL)4, which further assembles into 1D chiral crystals 3 or rare 3D crystals 4 of bpy-bridged 5-fold interpenetrating diamondoid architecture with metallacalix[4]arene building blocks as novel 4-connecting nodes, and the combination of CdII and HL forms an 8-connected C2-symmetric M4(HL)4 that fabricates the α-Po net of 5. Notably, those large M4(HL)4 units are potentially highly connected building blocks in a hierarchical assembly of metal−organic networks. Magnetic studies disclose antiferromagnetic interactions in M4(HL)4 of 1−4. The magnetic data for 1, 3, and 4, all containing isomeric Ni4(HL)4 units, are analyzed by an equilateral quadrangle isotropic model combined with the molecular-field approximation with J = −4.00(2), −3.39(2), and −2.72(3) cm−1, respectively, presenting a stronger comparison between the structure and magnetism. The emission of 5 is odd, which perhaps is relative to the bichelating fashion of ligand HL and a rare coordination geometry of CdII. Moreover, the thermal stability and gas sorption properties of these compounds were measured.
