MOFs with adequate free nitrogen sites have potential applications in dye adsorption and formic acid dehydrogenation. Here, we successfully synthesized a novel 3-D MOF 1 ([(CH)NH][Cd(L)DMA]·0.5DMA·1.
View Article and Find Full Text PDFSpectrochim Acta A Mol Biomol Spectrosc
May 2021
Porous coordination polymers with organic aminium as one of the guest species possess a potential application in dye adsorption and white-light material manufacture. Polycarboxylic acid with multiple COOH substituents tends to form this type of porous material (with metal ion). Here the solvothermal self-assembly between Cd and a hexacarboxylic acid creates such a porous material [(CH)NH][Cd(L)]·5DMF·3HO (HL = 3,4-di(3,5-dicarboxyphenyl)phthalic acid) 1.
View Article and Find Full Text PDFSimple room-temperature self-assemblies between Cd2+ salts, SCN- and bisimidazole molecules at pH = 2 created three new organically templated thiocyanatocadmates [H2(L1)][Cd(SCN)4]·H2O (L1 = 1,4-bis(1H-imidazol-1-yl)benzene) 1, [H2(L2)][Cd(SCN)4] (L2 = 1,3-bis(2-methylimidazol-1-yl)propane) 2, and [H2(L3)][Cd2(SCN)6] (L3 = 1,4-bis(2-methyl-1H-imidazol-1-yl)butane) 3. X-ray single-crystal diffraction analysis reveals that (i) in 1-3, the SCN- groups doubly bridge the Cd2+ centers to form different thiocyanatocadmates: a linear chain in 1; a zigzag chain in 2; and a 2-D layer network (63 net) in 3; and (ii) in 1, via Nbase-HNSCN interactions, the L1 molecules extend the thiocyanatocadmate chains into a 2-D supramolecular layer, whereas in 2, the zigzag thiocyanatocadmate chains self-assemble into a 3-D supramolecular network via weak SS interactions. Photoluminescence analysis indicates that the three title compounds all emit light: blue light for 1 and 2 and green light for 3.
View Article and Find Full Text PDFPhotochem Photobiol Sci
February 2019
Under hydro(solvo)thermal conditions, four organic bidentate bridging N,N'-donor ligands 1,3-bis(2-methylimidazol-1-yl)propane (L1), 4,4'-di(1H-imidazol-1-yl)-1,1'-biphenyl (L2), 1,2-bis(2-methyl-1H-imidazol-1-ylmethyl)benzene (L3) and 5,6,7,8-tetrahydroquinoxaline (L4) were employed to react with CuBr/CuI, generating four 2-D layered copper(i)-polymer coordination polymer materials [Cu2Br2(L1)] 1, [CuI(L2)] 2, [CuI(L3)] 3 and [CuI(L4)0.5] 4. In 1-4, different Cu-X motifs are found: a cubic Cu4Br4 core in 1; a castellated Cu-I single chain in 2; a rhombic Cu2I2 core in 3; and a staircase-like Cu-I double chain in 4.
View Article and Find Full Text PDFIn this article, three bisimidazole derivatives (1,4-bis(2-ethylimidazol-1-yl)butane, L1; 4,4'-di(1-imidazol-1-yl)-1,1'-biphenyl, L2'; and 1,3-bis(2-ethylimidazol-1-yl)propane, L3) were employed to solvothermally react with AgI in an acidic environment, creating three new 1-D chained iodoargentates [H(L1)][AgI]·DMF (DMF = ,'-dimethylformamide) 1, [L2][AgI] (L2 = 4,4'-di(1-imidazol-1-ium)-1,1'-biphenyl) 2, and [H(L3)][AgI] 3. L2 in 2 originated from the N-alkylation of L2' with the CHOH solvent. X-ray single-crystal diffraction analysis reveals that (i) in 1, Ag and I aggregate to form a 1-D tube-like iodoargentate, which exhibits the same topology as the carbon tube; (ii) the chain structure of the iodoargentate in 2 is based on a kind of trinuclear Ag-I cluster, which can be viewed as a segment of the classical cubic MI cluster; (iii) the chain structure of the iodoargentate in 3 is simple, which can be described as a linear arrangement of the AgI tetrahedra by sharing edges.
View Article and Find Full Text PDFSeven compounds based on [PWO] ({PW}) were successfully prepared and carefully characterized. [HCHN][Cu(2,2'-bpy)][HPWO]·2HO (bpy = bipyridine) (1) is constructed from {PW} bridged by [Cu(2,2'-bpy)]. [HCHN][Zn(2,2'-bpy)][HPWO]·4HO (1a) is isostructural and isomorphous with compound 1.
View Article and Find Full Text PDFFive new organic-inorganic hybrid compounds based on [PWO] (abbreviated as {PW}) and several types of transition metal complexes (TMCs) have been synthesized and characterized by IR, UV-Vis, XRD, cyclic voltammetry measurements and single crystal X-ray diffraction analysis. [Cu(phen)][Cu(phen)(HO)][Cu(phen)(HO)][PWO]·8HO (1) (phen = 1,10-phenanthroline) is a {PW} bi-supported complex of phen, while [Cu(2,2'-bpy)(HO)][Cu(2,2'-bpy)][PWO]·3.5HO (2) (2,2'-bpy = 2,2'-bipyridine) is a 1-D chain structure formed by {PW} and copper complexes of 2,2'-bpy.
View Article and Find Full Text PDFSpectrochim Acta A Mol Biomol Spectrosc
October 2016
By utilizing the hydrothermal in situ acylation of organic acids with N2H4, three acylhydrazidate-coordinated compounds [Mn(L1)2(H2O)2] (L1=2,3-quinolinedicarboxylhydrazidate; HL1=2,3-dihydropyridazino[4,5-b] quinoline-1,4-dione) 1, [Mn2(ox)(L2)2(H2O)6]·2H2O (L2=benzimidazolate-5,6-dicarboxylhydrazide; HL2=6,7-dihydro-1H-imidazo[4,5-g]phthalazine-5,8-dione; ox=oxalate) 2, and [Cd(HL3)(bpy)] (L3=4,5-di(3'-carboxylphenyl)phthalhydrazidate; H3L3=6,7-dihydro-1H-imidazo[4,5-g]phthalazine-5,8-dione; bpy=2,2'-bipyridine) 3, as well as two acylhydrazide molecules L4 (L4=oxepino[2,3,4-de:7,6,5-d'e']diphthalazine-4,10(5H,9H)-dione) 4 and L5 (L5=4,5-dibromophthalhydrazide; L5=6,7-dibromo-2,3-dihydrophthalazine-1,4-dione) 5 were obtained. X-ray single-crystal diffraction analysis reveals that (i) 1 only possesses a mononuclear structure, but it self-assembles into a 2-D supramolecular network via the NhydrazineH⋯Nhydrazine and OwH⋯Ohydroxylimino interactions; (ii) 2 exhibits a dinuclear structure. Ox acts as the linker, while L2 just serves as a terminal ligand; (iii) In 3, L3 acts as a 3-connected node to propagate the 7-coordinated Cd(2+) centers into a 1-D double-chain structure; (iv) 4 is a special acylhydrazide molecule.
View Article and Find Full Text PDFSpectrochim Acta A Mol Biomol Spectrosc
May 2016
A new 3-D Zn(2+) coordination polymer (CP) [(CH3)2NH2]3[Zn6(ox)4.5(trz)6]⋅4H2O (ox=oxalate; trz=1,2,4-triazolate) 1 was obtained by a simple solvothermal self-assembly. The crystal structural analysis demonstrates that the trz molecules link the Zn(2+) ions into a two-dimensional (2-D) layer network, which is based on the trinuclear Zn3(trz)6 clusters.
View Article and Find Full Text PDF5-(3',4'-Dicarboxylphenoxy)isophthalic acid (H L1) and 5-(2',3'-dicarboxylphenoxy)isophthalic acid (H L2) were reacted with Cd salt with/without the assistance of N-donor ligands, creating five 3D Cd coordination polymers [Cd (L1)(H O) ]⋅H O (1), [Cd (L1)(bpe)(H O)] (bpe=1,2-bis(4-pyridyl)ethene; 2), [Cd (L1)(bpa)(H O)] (bpa=1,2-bis(4-pyridyl)ethane; 3), [Cd (L1)(bpp)] (bpp=1,3-bis(4-pyridyl)propane; 4), and [Cd (L2)(bpp) (H O) ]⋅H O (5). Crystal-structure analysis reveals 1) in 1, phthalate moieties for L1 link Cd1 centers into a 1D slightly helical chain; Cd2 centers act as bridges, linking 1D helical chains into a 3D network with a (3,5)-connected topology; 2) in 2-4, although Cd centers were further modified by the introduction of organic bases, L1 molecules still link Cd centers into 3D networks, which can all be simplified as pcu topology; 3) in 2-4, phthalate moieties first link Cd centers into an oligomer, in which carboxylate-bridged discrete or rod-shaped secondary building units (SBUs) are found (tetranuclear SBU in 2 and 3, rod-shaped SBU in 4); and 4) in 5, L2 molecules link Cd centers into a 2D (4,4) net; introduced bpp molecules serve as pillar linkers, extending Cd -L2 layers into a 3D network of 5. The sensing abilities of 2-5 for nitrobenzene (NB) were investigated.
View Article and Find Full Text PDFSix new organic-inorganic hybrid compounds based on [XM12O40](4-) (X = heteroatom, M = metal atom), namely [Cu(pic)2][H2XM12O40]·2Hapy·2apy (X = Si, M = W for , X = Ge, M = W for and X = Si, M = Mo for ), [Cu(2,2'-bpy)2][Cu(2,2'-bpy)(H2O)][Cu(pic)2]0.5[XM12O40]·nH2O (X = Si, M = Mo, n = 0.5 for , X = Ge, M = W, n = 1 for ) and [Cu(phen)(H2O)]2[Cu(pic)2][GeW12O40]·2.
View Article and Find Full Text PDFWith various organic base molecules as the countercations, five new thiocyanatocadmates [H2(tmen)][Cd(SCN)4] (tmen = N,N,N',N'-tetramethylethylenediamine) 1, [H2(tmba)][Cd2(SCN)6] (tmba = N,N,N',N'-tetramethyl-1,4-butanediamine) 2, [H2(teen)][Cd2(SCN)6] (teen = N,N,N',N'-tetra-ethylethylenediamine) 3, [H(amp)][Cd(SCN)2(CH3COO)] (amp = 2-amino-6-methylpyridine) 4 and [H(abp)]4[Cd(SCN)4]SO4·H2O (abp = 2-amino-6-bromopyridine) 5, and one new chlorocuprate(II) [H2(cha)][CuCl4] (cha = 1,4-cyclohexanediamine) 6 were obtained from a series of simple room-temperature self-assemblies at pH = 2 or 6.5. X-ray single-crystal diffraction analysis reveals that (i) templated by [(CH3)2NH(CH2)2NH(CH3)2](2+) (H2(tmen)(2+)), the anion [Cd(SCN)4](2-) in 1 shows a 1-D linear single-chain structure, whereas templated by [(CH3)2NH(CH2)4NH(CH3)2](2+) (H2(tmba)(2+)), the anion [Cd2(SCN)6](2-) in 2 shows a 1-D linear double-chain structure.
View Article and Find Full Text PDFFive new organic–inorganic hybrid compounds based on the Keggin-type polyoxoanion [SiW12O40]4−, namely [Cu3(2,2′-bpy)3(inic)(μ2-OH)(H2O)][SiW12O40]·2H2O (1), [Cu6(phen)6(μ3-Cl)2(μ2-Cl)2Cl2(inic)2][SiW12O40]·6H2O (2), [Cu2(hnic)(2,2′-bpy)2Cl]2[H2SiW12O40] (3), [Cu2(nic)(phen)2Cl2]2[SiW12O40] (4) and [Cu2(pic)(2,2′-bpy)2Cl]2[SiW12O40] (5) (inic = isonicotinic acid, hnic = 2-hydroxy-nicotinic acid, nic = nicotinic acid, pic = picolinic acid, 2,2′-bpy = 2,2′-bipyridine, phen = 1,10-phenanthroline) have been synthesized and characterized by IR, UV-Vis, XPS, XRD, cyclic voltammetric measurements, photoluminescence analysis and single crystal X-ray diffraction analysis. Crystal analysis reveals that compound 1 exhibits a 2-D double layered framework structure constructed from [SiW12O40]4− and copper-aqua-2,2′-bipy-hydroxyl-isonicotinate complexes. Compound 2 is a 0-D discrete structure formed by [SiW12O40]4− and copper-chloro-isonicotinate-phenanthroline complexes.
View Article and Find Full Text PDFUnder ambient conditions, reactions of CdCl2/Cd(CH3COO)2, SCN(-) and various organic amine molecules in strongly acidic solutions afforded the five new thiocyanatocadmates [H2(abpy)][CdCl2(SCN)2] (abpy = azobispyridine) 1, [H(apy)][Cd(SCN)3] (apy = 4-aminopyridine) 2, [H(ba)]2[CdCl2(SCN)2] (ba = tert-butylamine) 3, [H2(tmen)][Cd3Cl6(SCN)2] (tmen = N,N,N',N'-tetramethylethylenediamine) 4, and [H(dba)]2[Cd2(CH3COO)2(SCN)4] (dba = dibutylamine) 5. In compound 2 only, the CH3COO(-) ions in Cd(CH3COO)2 were completely displaced by SCN(-), producing a chained thiocyanatocadmate [Cd(SCN)3](-). In the other four compounds, the Cl(-) or CH3COO(-) ions appeared in the final inorganic anion frameworks.
View Article and Find Full Text PDFUnder hydro(solvo)thermal conditions, two 4-(4-carboxyphenoxy)phthalate-based three-dimensional (3-D) coordination polymers: [Cd3(cpph)2(bpa)2(H2O)]·0.5H2O (cpph = 4-(4-carboxyphenoxy)phthalate, bpa = 1,2-bis(4-pyridyl)ethane) 1, and [H2(bpp)][Mn2(cpph)2(H2O)2] (bpp = 1,2-bis(4-piperidyl)propane) 2 were isolated. In both compounds, the cpph molecules extend the metal ions into a 3-D network: a (4,6)-connected net for 1 and a simple 6-connected net with a pcu topology for 2.
View Article and Find Full Text PDFBy employing two types of hydrothermal in situ ligand reactions (acylation of N2H4 with aromatic polycarboxylic acids, reduction of 3-nitrophthalhydrazide by N2H4), three new acylhydrazidate-extended Zn(2+) coordination polymers [Zn2(3-apth)(atrz)2] (3-apth = 3-aminophthalhydrazidate; atrz = 3-amino-1,2,4-triazolate) 1, [Zn2(4-apth)(atez)2] (4-apth = 4-aminophthalhydrazidate; atez = 5-aminotetrazolate) 2, and [Zn(3-cppth)(H2O)] (3-cppth = 4-(3-carboxyphenoxy)phthalhydrazidate) 3 were obtained. X-ray single-crystal diffraction analysis revealed that (i) compound 1 possesses a 3-D structure. The triazolate molecules link the Zn(2+) ions to form a 2-D layer with a (6,3) topology.
View Article and Find Full Text PDFUnder hydrothermal conditions, the reactions of Ba(2+)/Zn(2+), aromatic polycarboxylic acids and N2H4 with or without oxalic acid were carried out, affording four new acylhydrazidate-extended metal-organic frameworks (MOFs) [Ba(pmdh)] (pmdh = pyromellitdihydrazidate) 1, [Ba(sdpth)(H2O)2]·0.5H2O (sdpth = 4,4'-sulfoyldiphthalhydrazidate) 2, [Ba2(cpth)2(H2O)2] (cpth = 4-carboxylphthalhydrazidate) 3 and [Zn2(pdh)2(ox)]·H2O (ox = oxalate, pdh = pyridine-2,3-dicarboxylhydrazidate) 4. The acylhydrazidate molecules pmdh, sdpth, cpth and pdh in compounds 1-4 derived from the hydrothermal in situ acylation of N2H4 with aromatic polycarboxylic acids.
View Article and Find Full Text PDFIn an acidic solution, the room-temperature reactions of CdX2 (X(-) = Cl(-), Br(-) or CH3COO(-)) and organic N-heterocyclic molecules with or without SCN(-)/SeCN(-)/dca(-) (dca(-) = dicyanamide) created the five new hybrid Cd(ii) compounds [H2(4,4'-dtdpy)]2[CdBr4]SO4·2.5H2O (dtdpy = dithiodipyridine) 1, [H(2,2'-dtdpy)]2[CdBr4] 2, [(Hbim)2CdCl2(SCN)2] (bim = 2,2'-biimidazole) 3, [H2(pip)][Cd(SCN)4] (pip = piperazine) 4 and [CdL2] (L = HNC(OH)N(-)CN) 5. X-ray single-crystal diffraction analysis revealed that: (i) compound 1 is a double salt of [H2(4,4'-dtdpy)]SO4 and [H2(4,4'-dtdpy)][CdBr4], [H2(4,4'-dtdpy)]SO4 shows a two-dimensional (2D) supramolecular layer structure and [H2(4,4'-dtdpy)][CdBr4] is distributed in the space between the supramolecular layers; (ii) compounds 2 and 3 are mononuclear molecular entities.
View Article and Find Full Text PDFBy employing the hydrothermal in situ acylation of N2H4 with aromatic polycarboxylic acids, three new acylhydrazidate-containing complexes [Zn(N2H4)(dphkh)]·H2O (dphkh = 4,4'-diphthalhydrazidatoketone hydrazone) 1, [Zn(npth)2] (npth = naphthalhydrazidate) 2 and [Mn(mpdh)2(H2O)2]·2H2O 4, and two new acylhydrazide molecules [bpth]·0.5H2O (bpth = 3,3'-biphthalhydrazide) 3 and [(chpth)2] (chpth = 4-chloro-5-hydrazinophthalhydrazide) 5 were obtained. It is noteworthy that (i) compound 1 is a layered Zn(2+) coordination polymer with a mixed ligand of dphkh and N2H4.
View Article and Find Full Text PDFThrough employing the hydrothermal in situ acylation of N2H4 with aromatic dicarboxylic acids, four new acylhydrazidate-coordinated complexes, [Cd2(pth)4(phen)2(H2O)2]·H2O (pth = phthalhydrazidate; phen = 1,10-phenanthroline) 1, [Cd3(dcpth)6(phen)2(H2O)2] (dcpth = 4,5-dichlorophthalhydrazidate) 2, [Cd(pdh)2(H2O)2] (pdh = pyridine-2,3-dicarboxylhydrazidate) 3 and [Pb(sdpth)(phen)] (sdpth = 4,4'-sulfoyldiphthalhydrazidate) 4, were obtained. X-ray analysis revealed that (i) isomerization and deprotonation of acylhydrazide molecules also occurred; (ii) compound 2 possesses a one-dimensional (1-D) double-chain structure, in which dcpth exhibits three types of coordination modes; (iii) compound 4 shows a 1-D castellated single-chain structure; (iv) the adjacent uncoordinated acylamino groups form a hydrogen-bonded dimer, via which compounds 2-4 self-assemble into different two-dimensional (2-D) supramolecular networks. In the solid state, only compound 3 emits green light (λ(em) = 525 nm), while in an aqueous solution, compounds 1, 3 and 4 all emit light.
View Article and Find Full Text PDFA compound containing the first [V16O39Cl](6-) (V16O39) polyanion has been hydrothermally synthesized and characterized.
View Article and Find Full Text PDFWith diverse multi-dentate N-heterocyclic/diamine molecules as the cations, the reactions between Cd(2+) and SCN(-) in C2H5OH/H2O solution acidified by H2SO4 created five new thiocyanatocadmates [H2(bim)][Cd(SCN)2(H2O)2]SO4 (bim = 2,2'-biimidazole) 1, [H2(pympip)]2[Cd2(SCN)4(SO4)2(H2O)4]·2H2O (pympip = 1-(2-pyrimidyl)piperazine) 2, [H2(tdpy)]2[Cd3(SCN)10] (tdpy = 4,4'-thiodipyridine) 3, [H2(badpm)][Cd(SCN)4] (badpm = 4,4'-biaminodiphenylmethane) 4 and [H2(pdma)][Cd2(SCN)4(SO4)] (pdma = 1,4-phenylenedimethanamine) 5. It is noteworthy that (i) in compounds 1, 2 and 5, SO4(2-) was incorporated into the organically templated thiocyanatocadmate frameworks; (ii) compound is a rare example, in which two types of chained thiocyanatocadmates are found, and (iii) compound shows an interesting layer structure, constructed up from the ribboned thiocyanatocadmates by μ2-mode SO4(2-). Photoluminescence analysis revealed that compounds 1, 2 and 5 in solid state emit blue light with the maximum at 425 nm for 1, 405 nm for 2 and 445 nm for 5, respectively.
View Article and Find Full Text PDFThe simple hydrothermal self-assemblies between metal salts, organic polycarboxylic acids and N(2)H(4)·H(2)O, sometimes in the presence of phenanthroline (phen), created four di(mono)acylhydrazidate-coordinated compounds [Pb(2)(DPHKH)(2)(phen)(2)]·2H(2)O 1, [Cd(ODPTH)(phen)]·0.25H(2)O 2, [Pb(2)(MPTH)(4)(phen)(2)] 3, [Cd(2)(MPTH)(4)(phen)(2)]·H(2)O 4 as well as one diacylhydrazide molecule [H(2)(ODPTH)] 5 (DPHKH = 4,4'-diphthalhydrazidatoketone hydrazone, MPTH = 3-methylphthalhydrazidate, ODPTH = 4,4'-oxydiphthalhydrazidate). Note that the di(mono)acylhydrazidate molecules in the title compounds originated from the in situ acylation reactions between organic polycarboxylic acids and N(2)H(4)·H(2)O.
View Article and Find Full Text PDFBy the simple hydrothermal self-assembly, four new monoacylhydrazidate-coordinated compounds [Mn(APTH)(2)(H(2)O)] 1, [Pb(APTH)(2)]·0.25H(2)O 2, [Pb(2)(EPDH)(4)(H(2)O)] 3 and [Pb(MPDH)(2)] 4 (APTH = 3-aminophthalhydrazidate, EPDH = 5-ethylpyridine-2,3-dicarboxylhydrazidate, MPDH = 6-methylpyrinde-2,3-dicarboxylhydrazidate) were obtained. It is noteworthy that APTH was derived from the in situ reduction reaction of NPTH (3-nitrophthalhydrazide) with N(2)H(4)·H(2)O as the reducer, whereas EPDH and MPDH were derived respectively from the in situ acylation reactions of epdca and mpdca (epdca = 5-ethylpyridine-2,3-dicarboxylic acid, mpdca = 6-methylpyridine-2,3-dicarboxylic acid) with N(2)H(4)·H(2)O.
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