Synthesis, structure and characterization of the trinuclear copper (I) complex [Cu3(μ3-Br)2(dppm)3]Br (original) (raw)
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Inorganica Chimica Acta, 2005
The hydrothermal reaction of La 2 O 3 and Pr 2 O 3 with pyridine-2,6-dicarboxylic acid (H 2 pydc), CuO, and H 2 O with a mole ratio of 1:2:4:300 resulted in the formation of two polymeric Cu(II)-Ln(III) complexes, [{Ln 4 Cu 2 (pydc) 8 (H 2 O) 8 } AE 18H 2 O] n (Ln = La (1); Pr (2)). 1 and 2 are isomorphous and crystallize in monoclinic space group C2/c. Complexes 1 and 2 have one-dimensional infinite chains with ''1'' shape. The 1D chains are linked by the hydrogen bonds and pÁ Á Áp stacking interactions to form layer structures which are further linked by the hydrogen bonds and pÁ Á Áp stacking interactions to form the three-dimensional (3D) structures with nanoscale porosities. Temperature-dependent magnetic susceptibilities and the thermal stabilities of complexes 1 and 2 were studied.
CrystEngComm, 2015
In this article, the synthesis, structural studies, and luminescence properties of Cu I , Ag I , and Au I complexes of pyrimidine-based phosphine [C 4 H 3 N 2-2-NH(CH 2 PPh 2)] (1) are described. The reactions of 1 with CuX led to the isolation of one-dimensional (1D) chain, tetranuclear ladder, or cyclic derivatives. The structural features of these complexes are greatly influenced by the metal-to-ligand ratio, reaction conditions, and CuX (X = Cl, Br or I) employed. In the case of CuCl and CuBr, one-dimensional coordination polymers [{CuCl}{C 4 H 3 N 2-2-NH(CH 2 PPh 2)}] ∞ (2) and [{CuBr}{C 4 H 3 N 2-2-NH(CH 2 PPh 2)}] ∞ (3) were obtained, whereas CuI afforded tetracopper complex [{CuI} 4 {C 4 H 3 N 2-2-NH(CH 2 PPh 2)} 2 (NCCH 3) 2 ] (4) having Cu 4 ladder structure supported by P∩N-bridging coordination of 1. The reaction of 1 with AgOTf yielded unprecedented one-dimensional chain structure [{AgOTf}{C 4 H 3 N 2-2-NH(CH 2 PPh 2)}] ∞ (5), whereas the reaction with AgBF 4 produced a 12-membered dinuclear complex, [{Ag}{C 4 H 3 N 2-2-NH(CH 2 PPh 2)}] 2 [BF 4 ] 2 (6), with each silver atom having a linear geometry. Gold complex [{AuCl}-{C 4 H 3 N 2-2-NH(CH 2 PPh 2)}] 2 (7) was synthesized by reacting 1 with [AuCl(SMe 2)]. Compounds 2−4 were also prepared using a pestle and mortar by grinding method in almost quantitative yield. Complex 4 with a Cu•••Cu distance of 2.828(5) Å shows high luminescence due to the nonbonded metal•••metal interactions.
Inorganica Chimica Acta, 2010
Hydrothermal synthesis has afforded a series of divalent copper coordination polymers with substituted glutarate ligands and the rigid rod tether 4,4 0 -bipyridine (bpy): {[Cu(Hdmg) 2 (bpy)]ÁH 2 O} n (1, dmg = 3,3dimethylglutarate), {[Cu 2 (dmg)(bpy) 2 ](ClO 4 )] n (2), [Cu 2 (emg) 2 (bpy)] n (3, emg = 3-ethyl, 3-methylglutarate) and [Cu 2 (cda) 2 (bpy)] n (4, cda = 1,1-cyclopentanediacetate). All materials were characterized by single-crystal X-ray diffraction. Compound 1 manifests l 2 -oxygen bridged [Cu 2 (Hdmg) 4 ] ''X"-patterns connected into a ribbon motif by bpy linkers. On the other hand, 2 possesses mixed-valence [Cu I Cu II Cu II-Cu I ] tetrameric clusters bridged by dmg ligands and pillared into an 8-connected body-centered cubic (bcu) cationic lattice by bpy linkers. Compounds 3 and 4 are structurally very similar, displaying chain motifs with {Cu 2 (CO 2 ) 4 } paddlewheels connected by dicarboxylates, in turn conjoined into (4,4)-grid coordination polymer layers by bpy tethers. Variable temperature magnetic data indicate the presence of very strong antiferromagnetic coupling within the {Cu 2 (CO 2 ) 4 } paddlewheels in the latter two complexes, with g = 2.30(2) and J = À352(3) cm À1 for 3 and g = 2.35(2) and J = À352(5) cm À1 for 4. Significant structural contrasts are evident when compared to previously reported divalent copper/4,4 0 -bipyridine coordination polymers with unsubstituted or 2-methyl substituted glutarate ligands.
Inorganic Chemistry, 2006
The use of a strategy combining ligand design and changes of reaction conditions has been investigated with the goal of directing the assembly of mononuclear, dinuclear, tetranuclear, and polymeric copper(II) complexes. As a result, closely related copper monomers, alkoxo dimers, and hydroxo cubanes, along with a carbonate-bridged polymeric species, have been synthesized using the rigid, aliphatic amino ligands cis-3,5-diamino-transhydroxycyclohexane (DAHC), cis-3,5-diamino-trans-methoxycyclohexane (DAMC), and the glutaryl-linked derivative glutaric acid bis-(cis-3,5-diaminocyclohexyl) ester (GADACE). The composition of the monomeric complex has been determined by X-ray crystallography as [Cu 2 ](ClO 4 ) 2 (1), the two dimers as [{Cu(DAHC)(OMe)} 2 ]-(ClO 4 ) 2 ‚MeOH (2) and [{Cu(DAMC)(OMe)(ClO 4 )} 2 ] (3), the three Cu 4 O 4 cubanes as [{Cu(DAHC)(OH)} 4 ](ClO 4 ) 4 ‚ 2.5MeOH (4), [{Cu(DAMC)(OH)} 4 ](ClO 4 ) 4 ‚H 2 O (5), and [{Cu 2 (OH) 2 (GADACE)} 2 ]Cl 4 ‚2MeOH‚6H 2 O (6), and an infinitechain structure as [{Cu(DAHC)(CO 3 )} n ] . Furthermore, the cubane structures 4 and 5 have been investigated magnetically. Our studies indicate that formation of the monomeric, dimeric, and tetranuclear DAHC and DAMC complexes can be controlled by small changes in reaction conditions and that further preorganization of the ligand moiety by linking the DAHC cores (GADACE) allows more effective direction of the self-assembly of the Cu 4 O 4 cubane core.
Polyhedron, 2010
The coordination geometry and supramolecular structures of three copper(II) complexes of two ahydroxycarboxylates and one a-methoxycarboxylate with nitrogen donor co-ligands are discussed. The complexes have been characterized by elemental analysis, ESI-MS, IR and electronic spectroscopy, thermogravimetric analysis and magnetic measurements. The X-ray structure analysis of all the complexes, namely [(BPCA)Cu II (MA)] (1), [(BPCA)Cu II (MPA)(H 2 O)] (2) and [(BPCA)Cu II (BA)] n (3), where BPCA = bis(2pyridylcarbonyl)amidate, MA = racemic mandelate, MPA = racemic a-methoxy phenylacetate and BA = benzilate anion, shows the copper(II) ion in a distorted square-pyramidal geometry. In 1 the mandelate anion is coordinated to the copper(II) center in a bidentate fashion while in 2 the a-methoxycarboxylate is monodentate. In both cases a one-dimensional supramolecular array is formed through hydrogen bonds: the mononuclear units are directly connected in 1 by the MA hydroxyl group, whereas in 2 is the coordinated water that operates as H donor towards the MPA carboxylate group and the BPCA carbonyl oxygens of nearby complexes. In 3 the benzilate anion, acting as bridging ligand between copper ions, gives rise to a one-dimensional coordination polymer. In the latter, intra-and inter-chain pÁ Á Áp stacking interactions between pyridines and one phenyl ring of benzilate anions are observed in the packing.
Construction of novel coordination polymers with simple ligands
Transition Metal …, 2008
Three different types of metal-organic polymers have been prepared by a solution diffusion process carried out at room temperature. Crystals of the copper coordination polymers [CuX(4,4 0 -bipy)] n (X = Cl, Br, I) have been obtained by the reaction of 4,4 0 -bipyridine ligands with Cu 2 X 2 fragments to yield a three-dimensional network consisting of four interlocking planar lattices. Single crystals of [Cu 2 (1,2,4,5-BTC)(DMF) 2 ] n (1,2,4,5-BTC = 1,2,4,5-benzene tetracarboxylate) have been grown by slow diffusion from solutions of a mixture of CuBr 2 , 2,2 0 -dithiosalicylic acid, and sodium azide plus a mixture of 1,2,4,5-H 4 BTC and 4-cyanopyridine. The complex [Co(1,3,5-BTC)(4,4 0 -bipy)] n (1,3,5-BTC = 1,3,5-benzene tricarboxylate) has a 3D open framework structure involving terminal cobalt atoms plus bridging 1,3,5-BTC and 4,4 0 -bipyridine ligands.
Polyhedron, 2001
The neutral polymeric complexes of copper(II) [CuL 2 (4,4%-bipy)] n , where L is an a-hydroxycarboxylato ligand, lactate in 1, 2-methyllactate in 2, were prepared and characterised structurally. The copper atom is in an elongated tetragonally distorted octahedral environment in both compounds. Both a-hydroxycarboxylato ligands are O,O%-bidentate chelating monoanions and 4,4%-bipyridine acts as an N,N%-bis(monodentate) bridging ligand creating a linear polymeric arrangement. The polymeric chains are interconnected by O hydroxyl H···O carboxy hydrogen bonds in a way that creates cavities that differ in size between 1 and 2. Spectroscopic data are presented and discussed.
Inorganic Chemistry, 2009
0 -1,3-phenylenebis-(oxamate), ppba = N,N 0 -1,4-phenylenebis(oxamate), Me 4 en = N,N,N 0 ,N 0 -tetramethylethylenediamine, and dipn = dipropylenetriamine] have been synthesized and structurally and magnetically characterized. Complexes 1-6 have been prepared following a molecular-programmed self-assembly method, where a heteropolytopic tetranucleating phenylenedioxamato bridging ligand (L = mpba or ppba) is bound to four metal ions of identical or different natures (M = Cu II and/or Ni II ) with partially blocked coordination sites by bi-or tridentate polyamine terminal ligands (L 0 = Me 4 en or dipn). The structures of 1-6 consist of cationic tetranuclear Cu II 2 M II 2 entities with an overall 4 R rack-type architecture, which is made up of two oxamato-bridged homo-(1-5) or heterodinuclear (6) Cu II M II units (M = Cu and Ni) connected through either a meta-(1, 2, and 4) or a para-substituted (3, 5, and 6) phenylene spacer between the Cu II ions. The magnetic properties of 1-6 have been interpreted according to their "dimer-of-dimers" structure [H = -J(S 1 3 S 2 + S 3 3 S 4 ) -J 0 (S 1 3 S 3 ) with S 1 = S 3 = S Cu = 1/2 and S 2 = S 4 = S M = 1/2 (M = Cu) or 1 (M = Ni)]. The homometallic Cu II 4 complexes exhibit either strong (-J = 330-350 cm -1 ) or weak-to-moderate (-J = 4.8-87.1 cm -1 ) antiferromagnetic intradimer couplings through the oxamato bridge, depending on the bi-(1-3) or tridentate (4 and 5) nature of the terminal ligand, respectively. The heterometallic Cu II 2 Ni II 2 complex with a tridentate terminal ligand (6) shows instead a moderate antiferromagnetic intradimer coupling (-J = 50 cm -1 ). Otherwise, the nature and magnitude of the interdimer coupling cannot be unambiguously determined except for the pair of homo-and heterometallic Cu II 2 M II 2 complexes [M = Cu (5) and Ni ] with the p-phenylenedioxamato bridging ligand and a tridentate terminal ligand, which show a weak antiferromagnetic interdimer coupling (-J 0 = 14 and 23 cm -1 ) across the para-substituted phenylene spacer.