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View along the crystallographic b axis. LHS: Arrangement of the macrocyclic Ag1 subunits (blue) along the Ag2 coordination chain (red). Nitrate counterions are represented in green. RHS: The topology of the network is shown whereby the trans-tach ligand is subsituted by a three coordinate node at the centroid of the cyclohexane ring. The helical channels are shown in pink and green and run parallel to the crystallographic b axis.
Source publication
Ligand-directed 2D and 3D Ag(I) coordination networks are self-assembled from the rigid, topologically related tri-amino ligands cis-3,5-diaminopiperidine (cis-dapi) and cis,trans-1,3,5-triaminocyclohexane (trans-tach), yielding two networks of differing dimensionality including a 3D network of unprecedented topology comprising helical channels.
Contexts in source publication
Context 1
... subunits are linked to Ag2 centres via the remaining trans amino group in axial position. Additionally, two helical channels are observed within the three dimensional coordination network along the crystallographic b axis. The nitrate counterions, located in the octagonal channels, form hydrogen bonded interactions with the primary amino groups (Fig. ...
Context 2
... with 1, the structure has a 3 : 3 (metal : ligand) composition but is connected in three dimensions. Each Ag(I) ion has a trigonal planar geometry while each ligand functions as a m 3 -bridging group with non-planar geometry; both the Ag(I) ion and ligand act as 3-connected nodes and form the unprecedented 3D binodal topology (4.8.10)(8.10 2 ) (Fig. 2, RHS). To understand this topology it is informative to consider the nets shown in Fig. 3. Fig. 3a shows a uniform 2D (4.8 2 ) topology, 5b in which every 3-connected node is shared by one tetragon and two octagons. Fig. 3b demonstrates a uniform 3D (10.3)-a topology 5 which could be described as one of the 'derivatives' of the 2D (4.8 2 ) ...
Context 3
... broken). However, alternative arrangements of breaking and re-crosslinking may lead to other 'derivatives'. In the case of 2, breaking half of the tetragons and subsequent crosslinking to neighbouring layers results in the new topology (Fig. 3c). The tetragonal and octagonal channels involving the broken sides are therefore individually helical (Fig. 2, ...
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The self-assembly of Pd 4 L 2 metallocylcic and Pd 6 L 3 trigonal prismatic assemblies are described. The selction of one species over the other has been achieved by carfeul choice of ancilliary ligands, which...
Citations
... In this respect, the inclusion of a cyclo- hexane backbone in a ligand can satisfy both of these de- mands. For instance, in previous studies we have shown that the complexation of cis,trans-1,3,5-triaminocyclohexane (trans-tach) yielded a range of interesting complexes includ- ing polynuclear clusters, [17] coordination networks, [18] and one-dimensional chain complexes. [19] Herein, we not only report an extension to these studies, but also start to follow the complexation reactions using mass spectrometry. ...
Linked-in: The rigid Schiff-base ligand cis,trans-1,3,5-tris(pyridine-2-carboxaldimino) cyclohexane (ttop) is synthesized, and its complexation to copper(II) salts at a range of stoichiometries is investigated crystallographically by using electrospray mass spectrometry. Further, in-situ mass spectrometry measurements allow the stepwise construction of the complexes to be observed.
cis,trans-1,3,5-Triaminocyclohexane (trans-tach) has been shown to be an excellent ligand in the synthesis of discrete complexes, molecular clusters, and infinite architectures. Herein, we report the Schiff-base derivitization of trans-tach to form cis,trans-1,3,5-tris (pyridine-2-carboxaldimino) cyclohexane (ttop), and the complexation of this ligand with copper(II) salts. The complexation reaction leads to the crystallization of transition-metal complexes with nuclearities of 1, 2, and 4, and the formation of the complexes can be followed stepwise, in real time, using electrospray mass spectrometry.
... A lot of honeycomb 2D Ag(i) coordination polymers have been synthesized according to the above strategies. [20,38,69,[102][103][104][105][106][107] For instance, we recently constructed a 2D network [Ag 2 (4,4bipy) 3 (MeCN) 2 ](SbF 6 ) 2 which exhibited (6,3) topology, unprecedented for the Ag(i)-bipy system (Fig. 7b). [108] As [73] another kind of topologically equivalent 2D (6,3) net, the brick wall structures [53,109] are closely related to honeycomb networks. ...
... On the other hand, the same connecting metal centres may offer various structurally related but topologically different 2D and 3D networks. For example, Cronin et al. [106] described the intrinsic relationship among the 2D (4,8 2 ) net and the 3D (10,3)-a and (4,8,10)(8,10 2 ) nets as shown in Fig. 8. All three nets are based on the three-connecting nodes, where different 3D structures can be generated from the 2D net in a 'line breaking and crosslinking' way. ...
The supramolecular chemistry of Ag(i) coordination assemblies continues to attract attention due to their versatile structural diversity and potential physical and chemical functions. This article provides a short review of recent advances in the design and construction of Ag(i) coordination polymers with special emphasis on the Ag(i) ion coordination geometry, ligand functionality, and supramolecular interactions. The potential functions of Ag(i) coordination polymers are briefly summarized.
We report two cationic silver‐based coordination polymers with N‐donating quinoxaline as the linker. [Ag(quinoxaline)⁺] [–O3S(CH2)2SO3–]0.5·2H2O (which we denote as SLUG‐37 for University of California, Santa Cruz, structure No. 37; quinoxaline = C8H6N2) and [Ag(quinoxaline)⁺][CH3CO2–] (SLUG‐38) were solved by single‐crystal X‐ray diffraction and further characterized by several solid‐state techniques. Both structures consist of cationic 1D Ag‐quinoxaline chains arranged into π‐stacked layers, with charge‐balancing anions residing in the interlamellar space. The materials can be synthesized hydrothermally as well as in higher yield by reflux or room temperature conditions. The luminescent behavior of SLUG‐37 exhibits a strong white emission making it potentially useful as white LEDs.
The new, tridentate, facially coordinating ligand 1,4-diazepan-6-amine (daza) has been prepared from ethane-1,2-diamine and 2,3-dibromo-1-propanol in a seven-step procedure with an overall yield of 22 %. The conformation of the free ligand has been elucidated by pH- and temperature-dependent 1H NMR spectroscopy and by a single-crystal X-ray structure analysis of H3dazaCl3·H2O. A twisted chair with a predominantly equatorial orientation of the primary amino group has been established for daza and its protonation products Hxdazax+ (1 ≤ x ≤ 3). The formation constants of [M(daza)]2+ and [M(daza)2]2+ have been determined in aqueous solutions for M = NiII, CuII, ZnII, CdII, and CoII by potentiometric and spectrophotometric measurements, and a remarkably high stability has been found for the bis complexes ML2 in comparison to the mono complexes ML. This effect is discussed in terms of the particular steric requirements of the daza ligand. [Cu(daza)Cl2], [Ni(daza)2]Cl2·3.2H2O and [Zn(daza)2]SO4·5H2O have been characterized by single-crystal X-ray analyses. Aerial oxidation of Co2+ in the presence of daza results in the formation of the inert[Co(daza)2]3+, which was isolated as a mixture of the cisand trans isomers. These two isomers were separated by chromatographic methods and identified by NMR spectroscopy and single-crystal X-ray structure analysis of cis-[Co(daza)2][ZnBr4]Br·H2O and trans-[Co(daza)2]3[ZnBr4]2Br5·4H2O. The redox potentials of [Ni(daza)2]3+/2+ (1.04 V vs. NHE) and [Co(daza)2]3+/2+ (–0.21 V vs. NHE) were determined by cyclic voltammetry. The values are slightly more positive than for corresponding complexes with related cyclic triamines. This effect is again discussed in terms of the particular steric requirements of these ligands.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)
A silver(I) coordination polymer with mixed 2,3,5,6‐tetrachloro‐1,4‐benzenedicarboxylate (BDC‐Cl 4 ) and 2,2′‐bipyridine (2,2′‐bpy) ligands, [Ag 2 (BDC‐Cl 4 )(2,2′‐bpy)] n ( 1 ), was synthesized and structurally characterized. Compound 1 features a robust three‐dimensional (3D) network, exhibiting a new (4,6)‐connected net with the Schläfli symbol of (3 ² · 4 ² · 5 · 6) 2 (3 ² · 4 ² · 5 ² · 8 ⁷ · 9 · 10). The photoluminescence properties of 1 were investigated in the solid state at room temperature.
Reactions of octahedral and tetrahedral chalcocyanide cluster complexes of Re with Cu2+ cations and 1,2S,3S,4-tetraaminobutane (Threo-tab) were used to synthesize and study the structures of the following six novel chiral complexes: [{Cu2(NH3)(Threo-tab)3}Re6S8(CN)6] ⋅ 3H2O (I) (where Threo is 1,2S,3S,4-tetraaminobutane), [{Cu2(NH3)(Threo-tab)3}Re6Se8(CN)6] ⋅ 2H2O (II), [{Cu(Threo-tab)}2Re6Te8(CN)6] ⋅ 13.5H2O (III), [{Cu(Threo-tab)}2Re4Te4(CN)12] ⋅ 6.5H2O (IV), [{Cu2(NH3)(Threo-tab)2}Re4Te4(CN)12] ⋅ 4H2O (V), and [{Cu(NH3)(Threo-tab)}]2[Re4S3.4Te0.6(CN)12] ⋅ 1.25H2O (VI). The structures of complexes I–IV contain extended channels of sufficiently large size capable of including “guest” molecules.
A family of divalent metal–organic coordination polymers (MOCPs) that contain a conformationally flexible N,N′-bis(2-pyrazinyl)piperazine (bpzp) ligand were reported. The MOCPs {[Cu(bpzp)2(NO3)2]·3H2O}n (1·3H2O), {[Co(bpzp)2(NCS)2]·CH2Cl2·2CH3OH}n (2·CH2Cl2·2CH3OH) and {[Ni(bpzp)2(NCS)2]n·4CH3OH}n (3·4CH3OH) possess nearly identical extended rhombic grid-like (4,4)-layered networks, of which the latter two are isostructural and isomorphous. These layers are stacked in an eclipsed AAA arrangement for 1 and in a stagered ABABAB arrangement for 2 and 3. This can be attributed to the different conformations of the bpzp ligand, namely a C-e,e-anti conformer observed in 1 and a C-a,a-anti conformer in 2 and 3. In the case of [Ni(bpzp)3(NO3)2]n (4) and [Cd(bpzp)3(ClO4)2]n (5), the bpzp ligand is present as both a bridged bismonodentate C-e,e-anti conformer and a terminal monodentate C-e,e-syn conformer, leading to the formation of nearly identical linear chain structures. On the other hand, the MOCP {[Cd2(bdc)2(bpzp)3(H2O)2]·H2O}n (6·H2O, bdc = 1,4-benzenedicarboxylate) exhibits a 2D honeycomb (6,3)-layer structure, comprised of 1D Cd(bdc)-chain subunits and C-a,a-anti configured bpzp linkages. The MOCP [Cd2(btec)(bpzp)]n (7, btec = 1,2,4,5-benzenetetracarboxylate) adopts an extended 3D network comprised of Cd(btec)-based layers and C-e,e-anti configured bpzp pillars. These materials are thermally stable at temperatures up to 200 °C. The photoluminescence properties of the free bpzp ligand and the cadmium derivatives were also examined.
Platinum chemistry contains many highlights. The elucidation of the biochemical activity of Pt complexes continues to be developed effectively by NMR spectroscopic studies. Griesser et al. (R. Griesser, G. Kampf, L. E. Kapinos, S. Komeda, B. Lippert, J. Reedijk and H. Sigel, Inorg. Chem., 2003, 42, 32, ref. 171) and Colonna et al. (G. Colonna, N. G. Di Masi, L. G. Marzilli and G. Natile, Inorg. Chem., 2003, 42, 997, ref. 174) provide good examples of this work. Among developments in organometallic chemistry, studies of Pt complexes of functionalised carbenes by Lin et al. (G. Lin, N. D. Jones, R. A. Gossage, R. McDonald and R. G. Cavell, Angew. Chem., Int. Ed. Engl., 2003, 42, 4054 and N. D. Jones, G. Lin, R. A. Gossage, R. McDonald and R. G. Cavell, Organometallics, 2003, 22, 2832, ref. 188) are specially noteworthy.
Netze mit Clustern als Spacern: Chirale, heterometallische Koordinationspolymere (siehe Bild) können gezielt durch Kombination des chiralen (2S,3S)-1,2,3,4-Tetraaminobutan-Liganden mit einem labilen zweiwertigen Übergangsmetallkation wie Cu2+ und einem mehrkernigen Rhenium-Chalkogenid-Cyano-Cluster erhalten werden.
Introduction Coordination Geometries of Ag+ Ions Ligands in Silver(I) Coordination Polymers Supramolecular Interactions and Counter Anions in Silver(I) Coordination Polymers One- to Three-Dimensional Coordination Polymers Based on Silver–Ligand Coordination Bonds Intertwining or Interpenetrating of Silver(I) Coordination Polymers Properties of Silver(I) Coordination Polymers References
