7424-45-5Relevant articles and documents
From Short-Bite Ligand Assembled Ribbons to Nanosized Networks in Cu(I) Coordination Polymers Built upon Bis(benzylthio)alkanes (BzS(CH2)nSBz; n = 1?9)
Fortin, Daniel,Harvey, Pierre D.,Knorr, Michael,Lapprand, Antony,Schlachter, Adrien,Strohmann, Carsten
supporting information, p. 3686 - 3708 (2020/03/19)
With the objective to establish a correlation between the spacer distance and halide dependence on the structural features of coordination polymers (CPs) assembled by the reaction between CuX salts (X = Cl, Br, I) and dithioether ligands BzS(CH2)nSBz (n = 1?9; Bz = benzyl), a series of 26 compounds have been prepared and structurally investigated. A particular attention has been devoted to the design of networks with extremely long and flexible methylene spacer units between the SBz donor sites. Under identical conditions, CuI and CuBr react with BzSCH2Bz (L1) affording respectively the one-dimensional (1D) CPs {Cu(μ2-I)2Cu}(μ-L1)2]n (CP1) and {Cu(μ2-Br)2Cu}(μ-L1)2] (CP2), which incorporate Cu(μ2-X)2Cu rhomboids as secondary building units (SBUs). The hitherto unknown architecture of two-dimensional (2D) layers obtained with CuCl (CP3) differs from that of CP1 and CP2, which bear inorganic ?Cl?Cu?Cl?Cu?Cl? chains interconnected through bridging L1 ligands, thus forming a 2D architecture. The crystallographic characterization of a 1D CP obtained by reacting CuI with 1,3-bis(benzylthio)propane (L2) reveals that [{Cu(μ2-I)2Cu}(μ-L2)2]n (CP4) contains conventional Cu2I2 rhomboids as SBUs. In contrast, unusual isostructural CPs [{Cu(μ2-X)}(μ2-L2)]n (CP5) and (CP6) are obtained with CuX when X = Br and Cl, respectively, in which the isolated Cu atoms are bridged by a single μ2-Br or μ2-Cl ion giving rise to infinite [Cu(μ2-X)Cu]n ribbons. The crystal structure of the strongly luminescent three-dimensional (3D) polymer [{Cu4(μ3-I)3(μ4-I)(μ-L3)1.5]n (CP7) issued from reacting 2 equiv of CuI with BzS(CH2)4SBz (L3) has been redetermined. CP7 features unusual [(Cu4I3)(μ4-I)]n arrays securing the 3D connectivity. In contrast, mixing CuI with an excess of L3 provides the nonemissive material [{Cu(μ2-I)2Cu}(μ-L3)2]n (CP8). Treatment of CuBr and CuCl with L3 leads to [{Cu(μ2-Br)2Cu}(μ-L3)2]n (CP9) and the 0D complex [{Cu(μ2-Cl)2Cu}(μ-L3)2] (D1), respectively. The crystallographic particularity for CP9 is the coexistence of two topological isomers within the unit cell. The first one, CP9-1D, consists of simple 1D ribbons running along the a axis of the unit cell. The second topological isomer, CP9-2D, also consists of [Cu(μ2-Br)2Cu] SBUs, but these are interconnected in a 2D manner forming 2D sheets placed perpendicular to the 1D ribbons. Four 2D CPs, namely, [{Cu4(μ3-I)4}(μ-L4)2]n (CP10), [{Cu(μ2-I)2Cu}(μ-L4)2]n (CP11), [{Cu(μ2-Br)2Cu}(μ-L4)2]n (CP12), and [{Cu(μ2-Cl)2Cu}(μ-L4)2]n (CP13), stem from the self-assembly process of CuX with BzS(CH2)6SBz (L4). A similar series of 2D materials comprising [{Cu4(μ3-I)4}(μ-L5)2]n (CP14), [{Cu(μ2-I)2Cu}(μ-L5)2]n (CP15), [{Cu(μ2-Br)2Cu}(μ-L5)2]n (CP16), and [{Cu(μ2-Cl)2Cu}(μ-L5)2]n (CP17) result from the coordination of BzS(CH2)7SBz (L5) on CuX. Ligation of CuX with the long-chain ligand BzS(CH2)8SBz (L6) allows for the X-ray characterization of the luminescent 2D [{Cu4(μ3-I)4}(μ-L6)2]n (CP18) and the isostructural 1D series [{Cu(μ2-X)2Cu}(μ-L6)2]n CP19 (X = I), CP20 (X = Br) and CP21(X = Cl). Noteworthy, BzS(CH2)9SBz (L7) bearing a very flexible nine-atom chain generated the crystalline materials 2D [{Cu4(μ3-I)4}(μ-L7)2]n (CP22) and the isostructural 1D series [{Cu(μ2-X)2Cu}(μ-L6)2]n CP23 (X = I), CP24 (X = Br), and CP25 (X = Cl), featuring nanometric separations between the cubane- or rhomboid-SBUs. This comparative study reveals that the outcome of the reaction of CuX with the shorter ligands BzS(CH2)nSBz (n = 1?4) is not predictable. However, with more flexible spacer chains BzS(CH2)nSBz (n = 6?9), a clear structural pattern can be established. Using a 1:1 CuX-to-ligand ratio, [{Cu(μ2-X)2Cu}(μ-L4?7)2] CPs are always formed, irrespectively of L4?L7. Employing a 2:1 CuX-tocontinued... ligand ratio, only CuI is able to form networks incorporating Cu4(μ3-I)4 clusters as SBUs. All attempts to construct polynuclear cluster using CuBr and CuCl failed. The materials have been furthermore analyzed by powder X-ray diffraction, Raman spectroscopy, and thermogravimetric analysis, and the photophysical properties of the emissive materials have been studied.
Novel dithioether-silver(I) coordination architectures: Structural diversities by varying the spacers and terminal groups of ligands
Li, Jian-Rong,Ba, Xian-He,Jiao, Jiao,Du, Wen-Ping,Xu, Xiu-Hua,Zhang, Ruo-Hua
, p. 464 - 474 (2007/10/03)
An investigation into the dependence of the framework formation of coordination architectures on ligand spacers and terminal groups was reported based on the self-assembly of AgClO4 and eight structurally related flexible dithioether ligands, RS(CH2)nSR (L an, R = ethyl group, Lbn, R = benzyl group, n = 1-4). Eight novel metal-organic architectures, [Ag(L a1)3/2ClO4]n (1a), [Ag2(La2)2(ClO4) 2]2 (2a), [AgLa3ClO 4]n (3a), {[Ag(La4) 2]ClO4}n (4a), [AgLb 1ClO4]2 (1b), [Ag(Lb 2)2]ClO4 (2b), {[Ag(Lb 3)3/2(ClO4)1/2](ClO 4)1/2}n(3b) and [Ag(Lb 4)3/2ClO4]n (4b), were synthesized and structurally characterized by X-ray crystallography. Structure diversities were observed for these complexes: 1a forms a 2-D (6,3) net, while 2a is a discrete tetranuclear complex, in which the Ag1 ion adopts linear and tetrahedral coordination modes, and the S donors in each ligand show monodentate terminal and μ2-S bridging coordination fashions; 3a has a chiral helical chain structure in which two homo-chiral right-handed single helical chains (Ag-La3-)n are bound together through μ2-S donors, and simultaneously gives rise to left-handed helical entity (Ag-S-)n. In 4a, left- and right-handed helical chains formed by the ligands bridging Ag1 centers are further linked alternately by single-bridging ligands to form a non-chiral 2-D framework. 1b has a dinuclear structure showing obvious ligand-sustained Ag Ag interaction, while 2b is a mononuclear complex; 3b is a 3-D framework formed by ClO4- linking the 2-D (6,3) framework, which is similar to that of 1a, and 4b has a single, double-bridging chain structure in which 14-membered dinuclear ring units formed through two ligands bridging two Ag 1 ions are further linked by single-bridging ligands. In addition, a systematic structural comparison of these complexes and other reported AgClO4, complexes of analogous dithioether ligands indicates that the ligand spacers and terminal groups take essential roles on the framework formation of the Ag1 complexes, and this present feasible ways for adjusting the structures of such complexes by modifying the ligand spacers and terminal groups.
Synthesis of Oxygen and Sulphur Containing Crown Compounds under Solid-Liquid Phase Transfer Catalysis
Singh, Paramjit,Kumar, Manoj,Singh, Harjit
, p. 861 - 862 (2007/10/02)
Sulphur containing crown compounds and podands have been synthesized by intermolecular nucleophilic displacements of tosylates with thiolate ions generated in situ under solid-liquid phase transfer catalysis.
