Co-reporter:Xing-Pu Lv, Dong-Hui Wei, and Guang Yang
Inorganic Chemistry September 18, 2017 Volume 56(Issue 18) pp:11310-11310
Publication Date(Web):September 5, 2017
DOI:10.1021/acs.inorgchem.7b01717
The first binary hexameric silver(I) pyrazolate (Ag6pz6) has been prepared, and X-ray analysis demonstrated that it takes a rare figure-eight shape (pz– = deprotonated tert-butyl 3,5-diphenyl-1H-pyrazole-4-carboxylate). The hexamer can be easily converted to its tetrameric isomer (Ag4pz4) by recrystallization from ether. On the basis of the 1H NMR and mass spectrometry measurements, it is conjectured that the hexamer, after dissolving in CHCl3, quickly achieves equilibrium with Ag4pz4 and Ag3pz3, with the equilibrium lying far to the side of smaller rings.
Co-reporter:Lu-Hui Li;Jin-Xue Zhang;Shao-Kang Jia
Transition Metal Chemistry 2016 Volume 41( Issue 1) pp:107-113
Publication Date(Web):2016 February
DOI:10.1007/s11243-015-0002-7
A semi-rigid bipyrazolyl ligand, 2,5-bis(4′-methylene-1H-3′,5′-diphenylpyrazole)thiophene (H2L), and two of its copper complexes have been prepared. X-ray analysis demonstrates that \( \left[ {{\text{Cu}}_{2}^{\text{II}} \left( {{\text{H}}_{2} {\text{L}}} \right)_{2} {\text{Cl}}_{4} } \right] \) (1) is dinuclear, while \( {\text{Cu}}_{6}^{\text{I}} {\text{L}}_{3} \) (2) exhibits a trigonal prismatic cage structure in which the cavities are partially filled by THF molecules. Complex 2 emits strong phosphorescence at 77 K with maxima at 493 and 588 nm, which are tentatively attributed to the excited states 3LMMCT and 3MM, respectively. Based on the structural data, it is likely that weak intratrimeric (rather than intertrimeric) CuI···CuI interactions are responsible for the cuprophilicity-dependent emissions.
Co-reporter:Jing-Huo Chen, Ya-Mei Liu, Jin-Xue Zhang, Yan-Yan Zhu, Ming-Sheng Tang, Seik Weng Ng and Guang Yang
CrystEngComm 2014 vol. 16(Issue 23) pp:4987-4998
Publication Date(Web):03 Mar 2014
DOI:10.1039/C4CE00029C
Six triangular silver(I) or gold(I) 4-chloro/iodo-3,5-diphenyl pyrazolates, as well as a triangular silver(I) 4-methyl-3,5-diphenyl pyrazolate, have been synthesized and structurally characterized by single-crystal X-ray diffraction. Comparison and inspection of the Ag/Au⋯Cl/I distances, geometries of C–Cl/I bonds with respect to the Ag3 or Au3 triangles, and crystal packing diagrams verify the existence of Ag3⋯Cl/I or Au3⋯I interactions in some of the structures of the trimers, which are strong enough to impart a substantial effect on the spatial arrangement of the trimers in their solid states. Density function theory (DFT) calculations on the trimers give the molecular electrostatic potential (MEP) surfaces and HOMO/LUMOs, which support that the observed M3⋯X structural motifs can be understood on the basis of a weak acid–base interaction having contributions from both ionic δ+⋯δ− attraction and covalent LUMO–HOMO overlap. Calculations also show the existence of the so-called “σ-hole” and the secondary effect to it on the halogen atoms; the structural roles played by them were discussed based on the crystal structures.
Co-reporter:Guo-Sheng Han;Wen-Bo Li;Yang Li;Peng-Cheng Duan
Journal of Cluster Science 2014 Volume 25( Issue 5) pp:1249-1262
Publication Date(Web):2014 September
DOI:10.1007/s10876-014-0703-7
Five silver(I) complex of 4-amino-3,5-dipropyl-4H-1,2,4-triazole (4-NH2-3,5-Pr2tz) or 4-amino-3,5-dibutyl-4H-1,2,4-triazole (4-NH2-3,5-Bu2tz), namely [Ag2(4-NH2-3,5-Bu2tz)2(NO3)2] (1), [Ag4(4-NH2-3,5-Pr2tz)6(NO3)2](NO3)2 (2), [Ag4(4-NH2-3,5-Pr2tz)6](ClO4)4 (3), [Ag4(4-NH2-3,5-Pr2tz)6](CF3SO3)4 (4) and [Ag4(4-NH2-3,5-Bu2tz)6](BF4)4 (5), have been prepared and structurally characterized by X-ray single crystal diffractions. Based on the structural data, a possible mechanism for the formation of Ag4tz6 cluster has been proposed, involving the formation of a dimer of dimer—(Ag2tz2)2, followed by the replacement of counterions by two additional triazoles.
Co-reporter:Peng-Cheng Duan, Zhao-Yang Wang, Jing-Huo Chen, Guang Yang and Raphael G. Raptis
Dalton Transactions 2013 vol. 42(Issue 42) pp:14951-14954
Publication Date(Web):28 Aug 2013
DOI:10.1039/C3DT51332G
Two neutral hexanuclear trigonal prismatic cage molecules have been synthesized by coupling two planar triangular M3pz3-panels, M = Cu(I) and Ag(I), in eclipsed geometry. The ∼230 Å3 cage volume can be either vacant or occupied by neutral guests. The crystal structures of the M6–cyclohexane and Ag6–S8 host–guest species have been determined.
Co-reporter:Ya-Mei Liu;Shi-Tu Yang;Ting-Ting Yan;Hui Yang;Xiu-Bao Wei
Transition Metal Chemistry 2013 Volume 38( Issue 5) pp:543-551
Publication Date(Web):2013 August
DOI:10.1007/s11243-013-9722-8
Three novel Ag(I) adducts with 4-amino-3,5-dicyclohexyl-1,2,4-triazole [4-NH2-3,5-(C6H11)2tz], namely {Ag2[4-NH2-3,5-(C6H11)2tz]2(NO3)2} (1), {Ag4[4-NH2-3,5-(C6H11)2tz]4(ClO4)2}(ClO4)2 (2), {Ag[4-NH2-3,5-(C6H11)2tz]3}(ClO4) (3), as well as one polymeric Ag(I) triazolate, {Ag3[3,5-(C6H11)2tz]2(NO3)}n (4), have been synthesized and characterized. X-ray analyses show that 1–3 are discrete dinuclear, cyclic tetranuclear and mononuclear complexes, featuring Ag2tz2, Ag4tz4 and Agtz3 structural motifs in turn. 4 is a 3D coordination polymer with the Ag4tz4 clusters as the secondary building unit, the ant network can be extracted from the structure of 4.
Co-reporter:Zhan-Dong Huang;Jun-Xian Chen;De-Liang Wang
Journal of Cluster Science 2013 Volume 24( Issue 1) pp:61-71
Publication Date(Web):2013 March
DOI:10.1007/s10876-012-0515-6
Reactions of silver(I) salts with 4-amino-3,5-diisobutyl-4H-1,2,4-triazole (4-NH2-3,5-iBu2-tz) or 4-amino-3,5-dibutyl-4H-1,2,4-triazole (4-NH2-3,5-Bu2-tz) yielded five new adducts, namely, [Ag2(4-NH2-3,5-iBu2-tz)2(NO3)2] (1), [Ag3(4-NH2-3,5-iBu2-tz)6](SO3CF3)3 (2), [Ag3(4-NH2-3,5-iBu2-tz)6](ClO4)3 (3), [Ag4(4-NH2-3,5-Bu2-tz)6](ClO4)4 (4) and [Ag4(4-NH2-3,5-Bu2-tz)6](CF3SO3)4 (5). X-ray analyses have been done on the first four adducts, showing that 1 and 4 adopt previously observed Ag2tz2 and Ag4tz6-a cluster structures, respectively; 2 and 3, on the other hand, contain an unprecedented Ag3tz6 cluster, which is closely related to Ag4tz6–a cluster by removal of one Ag atom from the latter. The formation of Ag3tz6 cluster other than the expected Ag4tz6 cluster in 2 and 3 has been tentatively attributed to the steric effect of isobutyl groups.
Co-reporter:Peng-Cheng Duan;Rui-Wen Jin;Zi-Xuan Wang
Journal of Chemical Crystallography 2013 Volume 43( Issue 8) pp:448-454
Publication Date(Web):2013 August
DOI:10.1007/s10870-013-0444-8
Reactions of a semirigid bipyrazole, 2,7-bis(4′-methylene-1H-3′,5′-diphenylpyrazole) naphthalene (H2L) with Ag(I) or Cu(II) salts yielded four dinuclear complexes, namely, [Ag2(H2L)2(NO3)2] (1), [Ag2(H2L)2](ClO4)2 (2), [Ag2(H2L)2](BF4)2 (3), and [Cu2(H2L)2Cl4] (4). X-ray analysis illustrates that the three Ag(I) complexes are structurally similar and exhibit a rectangular shape, while the Cu(II) complex features an intramolecular π-stacking between two naphthalene-moieties and is much more compressed compared with those Ag(I) complexes. Two different conformations, namely cis, cis- and trans, trans-, have been observed for this bipyrazolyl ligand in its Ag(I) and Cu(II) complexes, respectively.
Co-reporter:Guang Yang, Peng-Cheng Duan, Kai-Ge Shi, and Raphael G. Raptis
Crystal Growth & Design 2012 Volume 12(Issue 4) pp:1882-1889
Publication Date(Web):February 24, 2012
DOI:10.1021/cg201535x
Four isomers of 3,5-dibutyl-1H-1,2,4-triazole (3,5-R2tzH, R = butyl (nBu), isobutyl (iBu), secondary butyl (sBu), and tertiary butyl (tBu)) have been synthesized by condensation of the corresponding organic acids and hydrazine, followed by a deamination reaction. Their binary silver complexes have been prepared and structurally characterized by X-ray diffraction. [Ag(3,5-nBu2tz)]n and [Ag(3,5-iBu2tz)]n exhibit 3D structures of cds and dia topologies, respectively, while [Ag(3,5-sBu2tz)]n displays a 2D sql net and [Ag(3,5-tBu2tz)]4 is a 0D tetranuclear complex. Having the same empirical formula, these four binary silver triazolates are true isomers, differing in their linkage and triazole coordination modes. This work represents an interesting case in which ligand isomerism is manifested in the structures of the corresponding metal complexes.
Co-reporter:Wen-Hua Zhang;Yong-Hui Wang;Ya-Wei Li
Journal of Cluster Science 2012 Volume 23( Issue 2) pp:411-420
Publication Date(Web):2012 June
DOI:10.1007/s10876-012-0445-3
The Ag(I) and Cu(I) complexes of 4-amino-3,5-dipentyl-4H-1,2,4-triazole (4-NH2-3,5-(C5H11)2tz) and 3,5-dipentyl-1H-1,2,4-triazole (3,5-(C5H11)2tzH) have been synthesized and characterized. X-Ray analysis shows that {Ag4[4-NH2-3,5-(C5H11)2tz]6}(BF4)4 is a tetranuclear complex featuring an Ag4tz6 cluster; {Ag[3,5-(C5H11)2tz]}n exhibits a 3D structure of lvt-a topology; and {Cu2[3,5-(C5H11)2tz]Br}n is a Cu4Br4-cluster based 3D complex with the dia topology.
Co-reporter:Peng-Cheng Duan;Zhan-Dong Huang;Fang-Fang Zhang
Transition Metal Chemistry 2012 Volume 37( Issue 6) pp:595-600
Publication Date(Web):2012 September
DOI:10.1007/s11243-012-9627-y
A semirigid bipyrazolyl ligand, 4,4′-bis[(3″,5″-diethyl-1H-pyrazol-4″-yl)methylene)]-1,1′-biphenyl (H2L), and four of its Ag(I) and Cu(II) complexes have been prepared and structurally characterized. X-ray analysis demonstrates that the Ag(I) complexes are dinuclear molecular rectangle, while the Cu(II) complexes display a twisted rectangular structure. Two different conformations, namely cis and trans, have been observed for this bipyrazolyl ligand.
Co-reporter:Zhao-Yang Wang;Jing-Huo Chen;Ling-Fei Zhao;Wen-Hua Zhang
Transition Metal Chemistry 2011 Volume 36( Issue 7) pp:
Publication Date(Web):2011 October
DOI:10.1007/s11243-011-9526-7
Two semi-rigid bipyrazolyl ligands, namely 2,3,5,6-tetramethyl-1,4-bis[(3′,5′-dimethyl-1H -pyrazol-4′-yl)methylene]benzene (H2L) and 2,3,5,6-tetramethyl-1,4-bis[(3′,5′-diphenyl-1H -pyrazol-4′-yl)methylene]benzene (H2L′), and their Ag(I) and Cu(II) complexes have been prepared and structurally characterized by means of X-ray analysis. In the structures of the metal complexes, namely [Ag2(H2L)2](BF4)2·2H2O (1), [Ag(H2L)(NO3)]n (2), [Cu2(H2L)4(SO4)2]·11H2O (3), and {[Ag(H2L′)]BF4}n (4), the bipyrazoles act as bridging ligands to connect two metal atoms. Complexes 2 and 4 exhibit 1-D polymeric structures, while 1 and 3 are discrete molecules with a rectangular dimer or tetragonal prismatic shapes, respectively. Two different conformations, namely cis and trans, have been observed for these bipyrazolyl ligands.
Co-reporter:Wen-Hua Zhang;Xiu-Bao Wei;Ping-Ning Jin;Jun-Feng Kou
Transition Metal Chemistry 2011 Volume 36( Issue 5) pp:459-463
Publication Date(Web):2011 August
DOI:10.1007/s11243-011-9490-2
Reactions of 3(5)-methyl-5(3)-phenyl-1H-1,2,4-triazole (3-Me-5-Ph-tzH) with AgNO3 in the absence/presence of NH3 yield a mononuclear [Ag(3-Me-5-Ph-tzH)2]NO3·3H2O (1) and a polymeric [Ag(3-Me-5-Ph-tz)]n (2), respectively. Two structurally different infinite chains, however, with the same formula of AgC9H8N3—one is double-decked and the other single zigzag—coexist in 1:1 ratio in the crystal of 2. As far as we know, 2 is the first binary silver(I) complex based on an asymmetric triazole and represents a rare case of two supramolecular isomers coexisting in the same crystal.
Co-reporter:Guang Yang;Shu-Juan Hao;Zhao-Yang Wang
Transition Metal Chemistry 2010 Volume 35( Issue 3) pp:381-386
Publication Date(Web):2010 April
DOI:10.1007/s11243-010-9338-1
A semi-rigid bipyrazolyl ligand, namely 5-tert-butyl-1,3-bis[(3′,5′-diethyl-1H-pyrazol-4′-yl) methylene]benzene, and its Ag(I) and Cu(II) complexes have been prepared and structurally characterized. X-ray analysis demonstrates that the Ag(I) complex is based on a dinuclear molecular rectangle, while the Cu(II) complex displays a mono-strand helical structure. Two different conformations, namely cis,cis and cis,trans have been observed for this bipyrazolyl ligand.
Co-reporter:Jun-Feng Kou;Yu Zhu
Crystal Research and Technology 2009 Volume 44( Issue 7) pp:776-780
Publication Date(Web):
DOI:10.1002/crat.200900071
Abstract
Two polymorphs of silver 5-(3-aminophenyl)tetrazolates – α- and β-Ag(amphttz) have been obtained by the reaction of amphttzH with AgNO3 in presence of ammonia either in ambient condition or under the hydrothermal condition, respectively (amphttzH = 5-(3-aminophenyl)tetrazole). Both of the two phases of Ag(amphttz) were characterized by elemental analyses, IR spectra and single-crystal X-ray diffraction. X-ray analysis shows α-, β-phases crystallize in P -1 with a = 8.551 (2) Å, b = 8.720(2) Å, c = 11.173(2) Å, α = 98.15(3)°, β = 90.95(3)°, γ = 95.45(3)° and C 2/c with a = 13.542(3) Å, b = 10.135(2) Å, c = 12.610(3) Å, β = 113.58(3)°, respectively. The two polymorphs exhibit different 3D structures. (© 2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)
Co-reporter:Guang Yang;Ying-Li Wang;Li-Li Liu;Seik Weng Ng
Transition Metal Chemistry 2009 Volume 34( Issue 7) pp:751-755
Publication Date(Web):2009 October
DOI:10.1007/s11243-009-9258-0
Five silver(I) adducts of 4-amino-3,5-diethyl-4H-1,2,4-triazole (4-NH2-3,5-Et2-tz) or 4-amino-3,5-dimethyl-4H-1,2,4-triazole (4-NH2-3,5-Me2-tz), namely [Ag4(4-NH2-3,5-Et2-tz)6](ClO4)4 (1), [Ag(4-NH2-3,5-Et2-tz)2]n·n(ClO4) (2), [Ag4(4-NH2-3,5-Et2-tz)6](CF3SO3)4 (3), [Ag4(4-NH2-3,5-Me2-tz)6](ClO4)4·4H2O (4) and [Ag4(4-NH2-3,5-Me2-tz)6](CF3SO3)4·2H2O (5), have been prepared and structurally characterised by X-ray single crystal diffraction. Two types of Ag4tz6 cluster have been observed in the structures of compound 1, 3, 4 and 5, which is rationalised based on the minimisation of the steric repulsions between the substituents on the 3,5-positions of triazole ring. Compound 2 displays an infinite chain structure and may be an intermediate or a minor product in the preparation.
Co-reporter:Guang Yang;Ying-Li Wang;Jin-Peng Li;Yu Zhu;Shao-Min Wang;Hong-Wei Hou;Yao-Ting Fan;Seik Weng Ng
European Journal of Inorganic Chemistry 2007 Volume 2007(Issue 5) pp:
Publication Date(Web):5 JAN 2007
DOI:10.1002/ejic.200600898
Reactions of silver salts with 4-amino-3,5-diisopropyl-1,2,4-triazole (L) afford dinuclear complex [Ag2L2(NO3)2(CH3CN)], triangular complex [Ag3L3](CF3SO3)3, and cyclic tetranuclear complexes [Ag4L6](BF4)4 and [Ag4L6](ClO4)4. On the basis of the X-ray analyses, anions are found to play an important role in determining the structures. Through coordination/noncoordination, anions can impart their influence on the coordination geometry of Ag atoms and the angles of N–Ag–N, which seems to be the main factor controlling the nuclearity of the reaction products in this system. 1H NMR and MS measurements suggest that these complexes probably retain their structural integrities in CH3CN solution. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)
Co-reporter:Guang Yang;Seik Weng Ng
Crystal Research and Technology 2007 Volume 42(Issue 2) pp:201-206
Publication Date(Web):11 JAN 2007
DOI:10.1002/crat.200610797
Lithium 3,5-dinitrobenzoate (Li(dnb)) exhibits a 1D propeller chain structure of D3 point symmetry and the chains are trigonally assembled in the crystal under the chiral space group P 3121. Sodium 3,5-dinitrobenzoate (Na(dnb)) also crystallizes in space group P 3121 and exhibits a 3D structure. The structure of Na(dnb) could be regarded to be similar to that of Li(dnb) if the weaker Na-O(nitro) bonds were to be ignored. These two compounds represent rare examples of octupoles arranged in an octupolar environment and show modest powder SHG effects. (© 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)
Co-reporter:Peng-Cheng Duan, Zhao-Yang Wang, Jing-Huo Chen, Guang Yang and Raphael G. Raptis
Dalton Transactions 2013 - vol. 42(Issue 42) pp:NaN14954-14954
Publication Date(Web):2013/08/28
DOI:10.1039/C3DT51332G
Two neutral hexanuclear trigonal prismatic cage molecules have been synthesized by coupling two planar triangular M3pz3-panels, M = Cu(I) and Ag(I), in eclipsed geometry. The ∼230 Å3 cage volume can be either vacant or occupied by neutral guests. The crystal structures of the M6–cyclohexane and Ag6–S8 host–guest species have been determined.
