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1.
Dr. Zhen‐Zhong Lu Rui Zhang Zhao‐Rui Pan Prof. Dr. Yi‐Zhi Li Zi‐Jian Guo He‐Gen Zheng 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(10):2812-2824
Five metal–organic frameworks (MOFs) formed by [WS4Cux]x?2 secondary building units (SBUs) and multi‐pyridyl ligands are presented. The [WS4Cux]x?2 SBUs function as network vertexes showing various geometries and connectivities. Compound 1 contains one‐dimensional channels formed in fourfold interpenetrating diamondoid networks with a hexanuclear [WS4Cu5]3+ unit as SBU, which shows square‐pyramidal geometry and acts as a tetrahedral node. Compound 2 contains brick‐wall‐like layer also with a hexanuclear [WS4Cu5]3+ unit as SBU. The [WS4Cu5]3+ unit in 2 is a new type of [WS4Cux]x?2 cluster unit in which the five Cu+ ions are in one plane with the W atom, forming a planar unit. Compound 3 shows a nanotubular structure with a pentanuclear [WS4Cu4]2+ unit as SBU, which is saddle‐shaped and acts as a tetrahedral node. Compound 4 contains large cages formed between two interpenetrated (10,3)‐a networks also with a pentanuclear [WS4Cu4]2+ unit acting as a triangular node. The [WS4Cu4]2+ unit in 4 is isomeric to that in 3 and first observed in a MOF. Compound 5 contains zigzag chains with a tetrahedral [WS4Cu3]+ unit as SBU, which acts as a V‐shaped connector. The influence of synthesis conditions including temperature, ligand, anions of CuI salts, and the ratio of [NH4]2WS4 to CuI salt on the formation of these [WS4Cux]x?2‐based MOFs were also studied. Porous MOF 3 is stable upon removal and exchange of the solvent guests, and when accommodating different solvent molecules, it exhibits specific colors depending on the polarity of incorporated solvent, that is, it shows a rare solvatochromic effect and has interesting prospects in sensing applications. 相似文献
2.
Olha Sereda Helen Stoeckli‐Evans 《Acta Crystallographica. Section C, Structural Chemistry》2008,64(6):m221-m223
The structure of the title compound, [NiCu(CN)4(C10H8N2)(H2O)2]n or [{Cu(H2O)2}(μ‐C10H8N2)(μ‐CN)2{Ni(CN)2}]n, was shown to be a metal–organic cyanide‐bridged framework, composed essentially of –Cu–4,4′‐bpy–Cu–4,4′‐bpy–Cu– chains (4,4′‐bpy is 4,4′‐bipyridine) linked by [Ni(CN)4]2− anions. Both metal atoms sit on special positions; the CuII atom occupies an inversion center, while the NiII atom of the cyanometallate sits on a twofold axis. The 4,4′‐bpy ligand is also situated about a center of symmetry, located at the center of the bridging C—C bond. The scientific impact of this structure lies in the unique manner in which the framework is built up. The arrangement of the –Cu–4,4′‐bpy–Cu–4,4′‐bpy–Cu– chains, which are mutually perpendicular and non‐intersecting, creates large channels running parallel to the c axis. Within these channels, the [Ni(CN)4]2− anions coordinate to successive CuII atoms, forming zigzag –Cu—N[triple‐bond]C—Ni—C[triple‐bond]N—Cu– chains. In this manner, a three‐dimensional framework structure is constructed. To the authors' knowledge, this arrangement has not been observed in any of the many copper(II)–4,4′‐bipyridine framework complexes synthesized to date. The coordination environment of the CuII atom is completed by two water molecules. The framework is further strengthened by O—H...N hydrogen bonds involving the water molecules and the symmetry‐equivalent nonbridging cyanide N atoms. 相似文献
3.
Klein N Senkovska I Baburin IA Grünker R Stoeck U Schlichtenmayer M Streppel B Mueller U Leoni S Hirscher M Kaskel S 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(46):13007-13016
A combination of topological rules and quantum chemical calculations has facilitated the development of a rational metal–organic framework (MOF) synthetic strategy using the tritopic benzene‐1,3,5‐tribenzoate (btb) linker and a neutral cross‐linker 4,4′‐bipyridine (bipy). A series of new compounds, namely [M2(bipy)]3(btb)4 (DUT‐23(M), M=Zn, Co, Cu, Ni), [Cu2(bisqui)0.5]3(btb)4 (DUT‐24, bisqui=diethyl (R,S)‐4,4′‐biquinoline‐3,3′‐dicarboxylate), [Cu2(py)1.5(H2O)0.5]3(btb)4 (DUT‐33, py=pyridine), and [Cu2(H2O)2]3(btb)4 (DUT‐34), with high specific surface areas and pore volumes (up to 2.03 m3 g?1 for DUT‐23(Co)) were synthesized. For DUT‐23(Co), excess storage capacities were determined for methane (268 mg g?1 at 100 bar and 298 K), hydrogen (74 mg g?1 at 40 bar and 77 K), and n‐butane (99 mg g?1at 293 K). DUT‐34 is a non‐cross‐linked version of DUT‐23 (non‐interpenetrated pendant to MOF‐14) that possesses open metal sites and can therefore be used as a catalyst. The accessibility of the pores in DUT‐34 to potential substrate molecules was proven by liquid phase adsorption. By exchanging the N,N donor 4,4′‐bipyridine with a substituted racemic biquinoline, DUT‐24 was obtained. This opens a route to the synthesis of a chiral compound, which could be interesting for enantioselective separation. 相似文献
4.
Chen Cao Shu-Jin Bao Dr. Xiao-Yan Tang Ze-Ming Xu Chun-Yan Ni Prof. Dr. Jian-Ping Lang 《化学:亚洲杂志》2021,16(18):2674-2680
Reactions of (NH4)2WS4 with CuCN, CuCN/1,2-bis(4-pyridyl)propane (bppa) or [Cu(MeCN)4]PF6/bppa under different reaction conditions afforded a set of two- or three-dimensional W/Cu/S cluster-based coordination polymers including {[Et4N]2[WS4Cu4(μ-CN)2(μ-I)2]}n ( 1 ), [WS4Cu4(μ-CN)2(bppa)2]n ( 2 ) and {[WS4Cu4(bppa)4](PF6)2}n ( 3 ), respectively. Compound 2 can be readily formed from reaction of 1 with bppa under solvothermal conditions. Compounds 1 and 2 feature two-dimensional networks with a “sql” topology, while 3 possesses a two-fold interpenetrated three-dimensional net with a rare “reo” topology. Compounds 1 – 3 in DMF exhibited different third-order nonlinear optical responses, and they all showed a reverse saturable absorption while 2 held a strong self-focusing effect. 相似文献
5.
First examples of transition metal complexes with HpicOH [Cu(picOH)2(H2O)2] ( 1 ), [Cu(picO)(2,2′‐bpy)]·2H2O ( 2 ), [Cu(picO)(4,4′‐bpy)0.5(H2O)]n ( 3 ), and [Cu(picO)(bpe)0.5(H2O)]n ( 4 ) (HpicOH = 6‐hydroxy‐picolinic acid; 2,2′‐bpy = 2,2′‐bipyridine; 4,4′‐bpy = 4,4′‐bipyridine; bpe = 1,2‐bis(4‐pyridyl)ethane) have been synthesized and characterized by single‐crystal X‐ray diffraction. The results show that HpicOH ligand can be in the enol or ketonic form, and adopts different coordination modes under different pH value of the reaction mixture. In complex 1 , HpicOH ligand is in the enol form and adopts a bidentate mode. While in complexes 2 – 4 , as the pH rises, HpicOH ligand becomes in the ketonic form and adopts a tridentate mode. The coordination modes in complexes 1 – 4 have not been reported before. Because of the introduction of the terminal ligands 2,2′‐bpy, complex 2 is of binuclear species; whereas in complexes 3 and 4 , picO ligands together with bridging ligands 4,4′‐bpy and bpe connect CuII ions to form 2D nets with (123)2(12)3 topology. 相似文献
6.
Mercury(II) complexes with 4,4′‐bipyridine (4,4′‐bipy) ligand were synthesized and characterized by elemental analysis, and IR, 1H‐ and 13C‐NMR spectroscopy. The structures of the complexes [Hg3(4,4′‐bipy)2(CH3COO)2(SCN)4]n ( 1 ), [Hg5(4,4′‐bipy)5(SCN)10]n ( 2 ), [Hg2(4,4′‐bipy)2(CH3COO)2]n(ClO4)2n ( 3 ), and [Hg(4,4′‐bipy)I2]n ( 4 ) were determined by X‐ray crystallography. The single‐crystal X‐ray data show that 2 and 4 are one‐dimensional zigzag polymers with four‐coordinate Hg‐atoms, whereas 1 is a one‐dimensional helical chain with two four‐coordinate and one six‐coordinate Hg‐atom. Complex 3 is a two‐dimensional polymer with a five‐coordinate Hg‐atom. These results show the capacity of the Hg‐ion to act as a soft acid that is capable to form compounds with coordination numbers four, five, and six and consequently to produce different forms of coordination polymers, containing one‐ and two‐dimensional networks. 相似文献
7.
Ying Wang Dr. Tian‐Wei Wang Hong‐Ping Xiao Yi‐Zhi Li Dr. You Song Xiao‐Zeng You Prof. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2009,15(31):7648-7655
By using cyclohexane‐1,2‐diamine (chxn), Ni(ClO4)2 ? 6H2O and Na3[Mo(CN)8] ? 4H2O, a 3D diamond‐like polymer {[NiII(chxn)2]2[MoIV(CN)8] ? 8H2O}n ( 1 ) was synthesised, whereas the reaction of chxn and Cu(ClO4)2 ? 6H2O with Na3[MV(CN)8] ? 4H2O (M=Mo, W) afforded two isomorphous graphite‐like complexes {[CuII(chxn)2]3[MoV(CN)8]2 ? 2H2O}n ( 2 ) and {[CuII(chxn)2]3[WV(CN)8]2 ? 2H2O}n ( 3 ). When the same synthetic procedure was employed, but replacing Na3[Mo(CN)8] ? 4H2O by (Bu3NH)3[Mo(CN)8] ? 4H2O (Bu3N=tributylamine), {[CuII(chxn)2MoIV(CN)8][CuII(chxn)2] ? 2H2O}n ( 4 ) was obtained. Single‐crystal X‐ray diffraction analyses showed that the framework of 4 is similar to 2 and 3 , except that a discrete [Cu(chxn)2]2+ moiety in 4 possesses large channels of parallel adjacent layers. The experimental results showed that in this system, the diamond‐ or graphite‐like framework was strongly influenced by the inducement of metal ions. The magnetic properties illustrate that the diamagnetic [MoIV(CN)8] bridges mediate very weak antiferromagnetic coupling between the NiII ions in 1 , but lead to the paramagnetic behaviour in 4 because [MoIV(CN)8] weakly coordinates to the CuII ions. The magnetic investigations of 2 and 3 indicate the presence of ferromagnetic coupling between the CuII and WV/MoV ions, and the more diffuse 5d orbitals lead to a stronger magnetic coupling interaction between the WV and CuII ions than between the MoV and CuII ions. 相似文献
8.
Auxilary Ligand Directed Zinc(II) Metal‐Organic Frameworks with Different Topological Networks
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Pingping Zhou 《无机化学与普通化学杂志》2017,643(4):325-329
By altering auxiliary N‐donor ligands, two ZnII compounds, [Zn3(HL)2(4,4′‐bipy)3]n ( 1 ) and [Zn4(L)2(bpp)]n ( 2 ) (H4L = 3‐(2′,4′‐dicarboxylphenoxy)phthalic acid, 4,4′‐bipy = 4,4′‐bipyridine, and bpp = 1,3‐bis(4‐pyridyl)propane), were obtained under hydrothermal conditions. Structural analyses revealed that compound 1 features a trinodal (3,4,4)‐connected 3D topological framework, and compound 2 displays a (3,8)‐connected 3D pillar‐layered framework with a tfz‐d topology. Furthermore, the thermal stabilities and the luminescent properties of compounds 1 and 2 were investigated. 相似文献
9.
Cationic (arene)ruthenium‐based tetranuclear complexes of the general formula [Ru4(η6‐p‐cymene)4(μ‐N∩N)2(μ‐OO∩OO)2]4+ were obtained from the dinuclear (arene)ruthenium complexes [Ru2(η6‐p‐cymene)2(μ‐OO∩OO)2Cl2] (p‐cymene=1‐methyl‐4‐(1‐methylethyl)benzene, OO∩OO=5,8‐dihydroxy‐1,4‐naphthoquinonato(2?), 9,10‐dihydroxy‐1,4‐anthraquinonato(2?), or 6,11‐dihydroxynaphthacene‐5,12‐dionato(2?)) by reaction with pyrazine or bipyridine linkers (N∩N=pyrazine, 4,4′‐bipyridine, 4,4′‐[(1E)‐ethene‐1,2‐diyl]bis[pyridine]) in the presence of silver trifluoromethanesulfonate (CF3SO3Ag) (Scheme). All complexes 4 – 12 were isolated in good yield as CF3SO salts, and characterized by NMR and IR spectroscopy. The host–guest properties of the metallarectangles incorporating 4,4′‐bipyridine and (4,4′‐[(1E)‐ethene‐1,2‐diyl]bis[pyridine] linkers were studied in solution by means of multiple NMR experiments (1D, ROESY, and DOSY). The largest metallarectangles 10 – 12 incorporating (4,4′‐[(1E)‐ethene‐1,2‐diyl]bis[pyridine] linkers are able to host an anthracene, pyrene, perylene, or coronene molecule in their cavity, while the medium‐size metallarectangles 7 – 9 incorporating 4,4′‐bipyridine linkers are only able to encapsulate anthracene. However, out‐of‐cavity interactions are observed between these 4,4′‐bipyridine‐containing rectangles and pyrene, perylene, or coronene. In contrast, the small pyrazine‐containing metallarectangles 4 – 6 show no interaction in solution with this series of planar aromatic molecules. 相似文献
10.
E. Yang Jian Zhang Yi‐Hang Wen Yu‐Biao Chen Yao Kang Zhao‐Ji Li Yuan‐Gen Yao 《Acta Crystallographica. Section C, Structural Chemistry》2004,60(6):m280-m282
The hydrothermal reaction of an aqueous solution of Cu(CH3COO)2·H2O, 1,2,4,5‐benzenetetracarboxylic acid and 4,4′‐bipyridine gave rise to the interesting title three‐dimensional polymer {[Cu6(btec)3(4,4′‐bpy)3(H2O)2]·2H2O}n (btec is 1,2,4,5‐benzenetetracarboxylate, C10H2O84−, and 4,4′‐bpy is 4,4′‐bipyridine, C10H8N2), in which each btec ligand links six copper(II) cations into a lamellar [Cu6(btec)3(H2O)2]n subpolymer framework. There are two distinct diamine units and two distinct carboxylate units, with one of each lying across an inversion centre. 相似文献
11.
《无机化学与普通化学杂志》2018,644(2):109-113
The 2D CuII metal‐organic framework [Cu2(bptc)(H2O)4]n · 4nH2O ( 1 ) (H4bptc = biphenyl‐2,2′,4,4′‐tetracarboxylic acid) was hydrothermally synthesized and characterized by single‐crystal X‐ray diffraction and magnetic measurements. In the structure, bptc4– serves as a twisted Π‐shaped organic building block to connect paddlewheel [Cu2(COO)4] dinuclear units and mononuclear units through 2‐/2′‐carboxylate and 4‐/4′‐carboxylate, respectively. According to the magnetic analysis using a dimer‐plus‐monomer model, strong antiferromagnetic coupling is operative within the dinuclear unit (J = –311 cm–1 based on H = –J S 1 S 2), and the compound behaves like a mononuclear molecule at low temperature. 相似文献
12.
Yi Han Nicholas F. Chilton Ming Li Chao Huang Prof. Hong Xu Prof. Hongwei Hou Boujemaa Moubaraki Stuart K. Langley Prof. Stuart R. Batten Prof. Yaoting Fan Prof. Keith S. Murray 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(20):6321-6328
From a predesigned grid, [CuII5CuI4L6] ? (I)2 ? 13 H2O ( 1 ), in which LH2 was a pyrazinyl‐triazolyl‐2,6‐substituted pyridine, we successfully synthesized an extended 3D complex, 1∞[{CuII5CuI8L6}{μ‐[CuI3(CN)6]}2 ? 2 CH3‐ CN] ( 2 ), that displayed unprecedented coexistence of all the five known coordination geometries of copper. Grid 1 displayed monovalent central metal exchange (CME) of CuI for AgI for the first time, as well as the formation of tri‐iodide in the crystalline state. These systems were investigated for their magnetic properties. Remarkably, grid 1 showed much higher catalytic activity than the Ag‐exchanged product for synthesis of a substituted triazole, 1‐benzyl‐4‐phenyl‐1H‐1,2,3‐triazole. 相似文献
13.
Wenjiang Huang Jinfang Zhang Jianghua Li Chi Zhang 《Acta Crystallographica. Section C, Structural Chemistry》2013,69(2):123-126
In the polymeric title compound, [CuI(C10H8N4)]n, the CuI atom is in a four‐coordinated tetrahedral geometry, formed by two I atoms and two pyridine N atoms from two different 4,4′‐(diazenediyl)dipyridine (4,4′‐azpy) ligands. Two μ2‐I atoms link two CuI atoms to form a planar rhomboid [Cu2I2] cluster located on an inversion centre, where the distance between two CuI atoms is 2.7781 (15) Å and the Cu—I bond lengths are 2.6290 (13) and 2.7495 (15) Å. The bridging 4,4′‐azpy ligands connect the [Cu2I2] clusters into a two‐dimensional (2‐D) double‐layered grid‐like network [parallel to the (10) plane], with a (4,4)‐connected topology. Two 2‐D grid‐like networks interweave each other by long 4,4′‐azpy bridging ligands to form a dense 2‐D double‐layered network. To the best of our knowledge, this interwoven 2‐D→2‐D network is observed for the first time in [Cu2I2]–organic compounds. 相似文献
14.
Kai‐Long Zhong Li Chen Lin Chen 《Acta Crystallographica. Section C, Structural Chemistry》2011,67(2):m62-m64
The title compound, [Cu2(SO4)2(C10H8N2)2(C2H6O2)2(H2O)2]n, contains two crystallographically unique CuII centres, each lying on a twofold axis and having a slightly distorted octahedral environment. One CuII centre is coordinated by two bridging 4,4′‐bipyridine (4,4′‐bipy) ligands, two sulfate anions and two aqua ligands. The second is surrounded by two 4,4′‐bipy N atoms and four O atoms, two from bridging sulfate anions and two from ethane‐1,2‐diol ligands. The sulfate anion bridges adjacent CuII centres, leading to the formation of linear ...Cu1–Cu2–Cu1–Cu2... chains. Adjacent chains are further bridged by 4,4′‐bipy ligands, which are also located on the twofold axis, resulting in a two‐dimensional layered polymer. In the crystal structure, extensive O—H...O hydrogen‐bonding interactions between water molecules, ethane‐1,2‐diol molecules and sulfate anions lead to the formation of a three‐dimensional supramolecular network structure. 相似文献
15.
Zhongfeng Li Jianbao Li Weiwei Fan Xiaonan Xue Rong Wang Yuhan Jiang Manhua Wu Qionghua Jin 《无机化学与普通化学杂志》2014,640(11):2261-2267
Six heterothiometalic clusters, namely, [WS4Cu4(dppm)4](ClO4)2 · 2DMF · MeCN ( 1 ), [MoS4Cu4(dppm)4](NO3)2 · MeCN ( 2 ) [MoS4Cu3(dppm)3](ClO4) · 4H2O ( 3 ), [WS4Cu3(dppm)3](NO3) · 4H2O ( 4 ), [WS4Cu3(dppm)3]SCN · CH2Cl2 ( 5 ), and [WS4Cu3(dppm)3]I · CH2Cl2 ( 6 ) [dppm = bis (diphenylphosphanyl)methane] were synthesized. Compounds 1 – 4 were obtained by the reactions of (NH4)2MS4 (M = Mo, W) with [Cu2(μ2‐dppm)2(MeCN)2(ClO4)2] {or [Cu(dppm)(NO3)]2} in the presence of 1,10‐phen in mixed solvent (CH3CN/CH2Cl2/DMF for 1 and 2 , CH2Cl2/CH3OH/DMF for 3 and 4 . Compounds 5 and 6 were obtained by one‐pot reactions of (NH4)2WS4 with dppm and CuSCN (or CuI) in CH2Cl2/CH3OH. These clusters were characterized by single‐crystal X‐ray diffraction as well as IR, 1H NMR, and 31P NMR spectroscopy. Structure analysis showed that compounds 1 and 2 are “saddle‐shaped” pentanuclear cationic clusters, whereas compounds 3 – 6 are “flywheel‐shaped” tetranuclear cationic clusters. In 1 and 2 , the MS42– unit (M = W, Mo) is coordinated by four copper atoms, which are further bridged by four dppm molecules. In compounds 3 – 6 , the MS42– unit is coordinated by three copper atoms and each copper atom is bridged by three dppm ligands. 相似文献
16.
The title compound, {[Cu(NH3)4][Cu(CN)3]2}n, features a CuI–CuII mixed‐valence CuCN framework based on {[Cu2(CN)3]−}n anionic layers and [Cu(NH3)4]2+ cations. The asymmetric unit contains two different CuI ions and one CuII ion which lies on a centre of inversion. Each CuI ion is coordinated to three cyanide ligands with a distorted trigonal–planar geometry, while the CuII ion is ligated by four ammine ligands, with a distorted square‐planar coordination geometry. The interlinkage between CuI ions and cyanide bridges produces a honeycomb‐like {[Cu2(CN)3]−}n anionic layer containing 18‐membered planar [Cu(CN)]6 metallocycles. A [Cu(NH3)4]2+ cation fills each metallocyclic cavity within pairs of exactly superimposed {[Cu2(CN)3]−}n anionic layers, but there are no cations between the layers of adjacent pairs, which are offset. Pairs of N—H...N hydrogen‐bonding interactions link the N—H groups of the ammine ligands to the N atoms of cyanide ligands. 相似文献
17.
《Acta Crystallographica. Section C, Structural Chemistry》2017,73(11):968-974
By using environmentally friendly K3[Co(CN)6] as a cyanide source, the solvothermal reaction of CuCl2 and tetrazole (Htta) led to a novel tetrazolate‐ and cyanide‐bridged three‐dimensional heterometallic CuII–CoIII complex, namely poly[[hexa‐μ2‐cyanido‐κ12C :N‐pentakis(μ3‐tetrazolato‐κ3N 1:N 2:N 4)cobalt(III)tetracopper(II)] monohydrate], {[CoIIICuII4(CHN4)5(CN)6]·H2O}n , (I). The crystal structure analysis reveals that it is the first example of a (6,8,8)‐connected three‐dimensional framework with a unique topology, constructed from anionic [Co(CN)6]3− and cationic [(Cu1)2(tta)2]2+ and [(Cu2Cu3)(tta)3]+ units through μ2‐cyanide and μ3‐tetrazolate linkers. The compound was further characterized by thermal analysis, vibrational spectroscopy (FT–IR), scanning electron microscopy/energy‐dispersive X‐ray spectroscopy (SEM–EDS) and magnetic measurements. The magnetic investigation indicates that the complex exhibits antiferromagnetic coupling between adjacent CuII cations. 相似文献
18.
Zhi‐Guo Zhong Yu‐Quan Feng Ping Zhang 《Acta Crystallographica. Section C, Structural Chemistry》2013,69(8):833-836
A novel copper–niobium oxyfluoride, {[Cu2(C10H7N2O)2][NbOF4]}n, has been synthesized by a hydrothermal method and characterized by elemental analysis, EDS, IR, XPS and single‐crystal X‐ray diffraction. The structural unit consists of one C2‐symmetric [NbOF4]− anion and one centrosymmetric coordinated [Cu2(obpy)2]+ cation (obpy is 2,2′‐bipyridin‐6‐olate). In the [NbOF4]− anion, each NbV metal centre is five‐coordinated by four F atoms and one O atom in the first coordination shell, forming a square‐pyramidal coordination geometry. These square pyramids are then further connected to each other via trans O atoms [Nb—O = 2.187 (3) Å], forming an infinite linear {[NbOF4]−}n polyanion. In the coordinated [Cu2(obpy)2]+ cation, the oxidation state of each Cu site is disordered, which is confirmed by the XPS results. The disordered Cu sites are coordinated by two N atoms and one O atom from two different obpy ligands. The [NbOF4]− and [Cu2(obpy)2]+ units are assembled via weak C—H...F hydrogen bonds, resulting in the formation of a three‐dimensional supramolecular structure. π–π stacking interactions between the pyridine rings [centroid–centroid distance = 3.610 (2) Å] may further stabilize the crystal structure. 相似文献
19.
《Acta Crystallographica. Section C, Structural Chemistry》2018,74(3):256-262
Using polynuclear metal clusters as nodes, many high‐symmetry high‐connectivity nets, like 8‐connnected bcu and 12‐connected fcu , have been attained in metal–organic frameworks (MOFs). However, construction of low‐symmetry high‐connected MOFs with a novel topology still remains a big challenge. For example, a uninodal 8‐connected lsz network, observed in inorganic ZrSiO4, has not been topologically identified in MOFs. Using 2,2′‐difluorobiphenyl‐4,4′‐dicarboxylic acid (H2L) as a new linker and 1,2,4‐triazole (Htrz) as a coligand, a novel three‐dimensional CdII–MOF, namely poly[tetrakis(μ4‐2,2′‐difluorobiphenyl‐4,4′‐dicarboxylato‐κ5O1,O1′:O1′:O4:O4′)tetrakis(N,N‐dimethylformamide‐κO)tetrakis(μ3‐1,2,4‐triazolato‐κ3N1:N2:N4)hexacadmium(II)], [Cd6(C14H6F2O4)4(C2H2N3)4(C3H7NO)4]n, (I), has been prepared. Single‐crystal structure analysis indicates that six different CdII ions co‐exist in (I) and each CdII ion displays a distorted [CdO4N2] octahedral geometry with four equatorial O atoms and two axial N atoms. Three CdII ions are connected by four carboxylate groups and four trz− ligands to form a linear trinuclear [Cd3(COO)4(trz)4] cluster, as do the other three CdII ions. Two Cd3 clusters are linked by trz− ligands in a μ1,2,4‐bridging mode to produce a two‐dimensional CdII–triazolate layer with (6,3) topology in the ab plane. These two‐dimensional layers are further pillared by the L2− ligands along the c axis to generate a complicated three‐dimensional framework. Topologically, regarding the Cd3 cluster as an 8‐connected node, the whole architecture of (I) is a uninodal 8‐connected lsz framework with the Schläfli symbol (422·66). Complex (I) was further characterized by elemental analysis, IR spectroscopy, powder X‐ray diffraction, thermogravimetric analysis and a photoluminescence study. MOF (I) has a high thermal and water stability. 相似文献
20.
Xue‐Ru Liu Cheng‐Qi Jiao Yin‐Shan Meng Hai‐Lang Zhu Wen‐Jing Jiang Wen Wen Liang Zhao Tao Liu 《无机化学与普通化学杂志》2019,645(4):428-432
Two tetranuclear cyanide‐bridged FeIII2NiII2 compounds [Ni2(L1)4Fe2(μ‐CN)4(CN)2(L2)2] · 2ClO4 · CH3OH · 4H2O ( 1 ) and [Ni2(L1)4Fe2(μ‐CN)4(CN)2(L3)2] · 2ClO4 ( 2 ) [L1 = 4,4′‐dichloro‐2,2′‐bipyridine; L2 = hydrotris(pyrazolyl)borate; L3 = tetrakis(pyrazolyl)borate] were synthesized. Magnetic measurements indicated that both two compounds showed single‐molecule magnet (SMM) behaviors with the relaxation energy barrier of Δ/kB = 68.9(8) K for 1 and 12.6(1) K for 2 . Magneto‐structural analysis indicated that the intermolecular interactions played an important part in the slow magnetic relaxation behaviors. 相似文献