Search results for "Paddle wheel"
showing 8 items of 8 documents
Ring opening polymerization of d,l-lactide and ε-caprolactone catalysed by (pyrazol-1-yl)copper(ii) carboxylate complexes
2021
1,2-Bis{(3,5-dimethylpyrazol-1-yl)methyl}benzene (L) reacts with [Cu(OAc)2] and C6H5COOH, 4-OH-C6H4COOH, 2-Cl-C6H4COOH and (3,5-NO2)2-C6H3COOH to afford the copper complexes [Cu2(C6H5COO)4(L)2] (1), [Cu2(4-OH-C6H4COO)4(L)2] (2), [Cu2(2-Cl-C6H4COO)4(L)2]n (3) and [Cu{(3,5-NO2)2-C6H3COO}2L]n (4) which are characterised by IR, mass spectrometry, elemental analyses, and X-ray crystallography. The structural data revealed two geometries that are adopted by the complexes: (i) paddle wheel in 1, 2·7H2O, 3 and (ii) regular chains in 3 and 4. Magnetic studies show strong antiferromagnetic couplings in the paddle wheel complexes and a weak antiferromagnetic coupling in the monometallic chain one. Cat…
Supramolecular Assembly of Organophosphonate Diesters Using Paddle-Wheel Complexes: First Examples in Porphyrin Series
2014
The reactions of dicopper tetrapivalate complex Cu2(μ-OOC-t-Bu)4(NCMe)2 (1) with triphenylphosphine oxide and diethyl phosphite allow paddle-wheel (PW) copper(II) complexes with phosphorus-containing axial ligands (2, 3) to be obtained. When meso-bis(diethoxyphosphoryl)porphyrins 4M were employed in this ligand exchange reaction, a series of one-dimensional (1D) homo- and heterometallic coordination polymers 5M composed of PW subunits and organophosphonate diesters were prepared and characterized by means of single crystal X-ray analysis. Planar porphyrinate 4Pd and nonplanar metalloporphyrinates 4Cu and 4Ni proved to be appropriate molecular structural blocks for assembly of coordination p…
Coordinating and hydrogen bonding ability of a bifunctional 2D paddle-wheel copper(II) coordination polymer
2015
abstract A new copper(II) complex of formula {[Cu 2 (H 2 btc) 2 (dmf) 2 ] 4dmf} n (1)[H 4 btc = 1,2,4,5-benzenetetracarb-oxylic acid, dmf = dimethylformamide] has been synthesised and its structure determined by X-raydiffraction. The structure displays a new square grid of ‘‘paddle-wheel’’ tetracarboxylate-bridgeddicopper(II) units with an intradimer copper–copper separation of 2.619(2) A. The dmf molecules areretained through weak axial coordinative bonds and hydrogen bonding interactions with the carboxylicgroups of the porous neutral network of 4 4 net topology. The magnetic behaviour of 1 corresponds to astrong antiferromagnetic coupling within each dicopper(II) unit (J = 343 cm 1 with …
Asymmetric and Symmetric Dicopper(II) Paddle-Wheel Units with Modified Nucleobases
2015
New copper(II) paddle-wheel complexes with different modified nucleobases and simple molecules in the axial positions have been prepared by direct reactions between copper(II) salts and the corresponding uracil- or thymine-1-acetic acids under inert atmosphere to produce the two homoleptic complexes, [Cu2(μ-OOCCH2-T)4(G)2] and [Cu2(μ-OOCCH2-U)4(G)2], and the heteroleptic one [Cu2(μ-OOCCH2-T)2(μ-OOCCH2-U)2(G)2] (where OOCCH2-T = thymine-1-acetate, OOCCH2-U = uracil-1-acetate, and G = dimethylformamide, water, dimethylacetamide, or dimethyl sulfoxide). Interestingly, the crystal structures of this family of closely related molecules present significant differences in their supramolecular arra…
Dinuclear palladium(ii) compounds with bridging cyclometalated phosphines. Synthesis, crystal structure and electrochemical study
2006
The structural characterization of bis-cyclometalated palladium(II) compounds of formula Pd2[(micro-(C6X4)PPh2]2(micro-O2CR)2 [X = H, R = CH3 (3), CF3 (4), C(CH3)3 (5) and C6F5 (6); X = F, R = CH3 (7) and CF3 (8)], has confirmed its paddle wheel structure with two palladium atoms bridged by two acetates and two metalated phosphines in a head-to-tail arrangement. The Pd...Pd distances are in the range 2.6779(16)-2.7229(8) A. Under cyclic voltammetric conditions, compounds 3-6, in CH2Cl2 solution, were found to undergo a reversible oxidation peak in the range of potential values 0.84-1.25 V. A second partially-reversible oxidation is observed at more positive potentials (1.37-1.55 V). For com…
Two copper complexes from two novel naphthalene-sulfonyl-triazole ligands: different nuclearity and different DNA binding and cleavage capabilities.
2013
[EN] Two novel naphthalene-sulfonyl-triazole ligands, 5-amino-N1-(naphthalen-3-ylsulfony1)-1,2,4-triazole (anstrz) and 3,5-diamino-N1-(naphthalen-3-ylsulfony1)-1,2,4-triazole (danstrz), purposely designed to interact with DNA, have been prepared for the first time and then fully characterized by H-1, C-13 NMR and IR spectroscopy, mass spectrometry and elemental analysis. The crystal structures of two copper complexes of these derivatives, i.e. [Cu(anstrz)(4)(NO3)(2)]center dot 4CH(3)OH (1), mononuclear, and [Cu(danstrz)(mu-OAc)(2)](2)center dot 2(danstrz) (OAc = acetato) (2), dinuclear, have been determined by single-crystal X-ray diffraction. In both cases the ligand coordinates in a monod…
Multitechnique Analysis of the Hydration in Three Different Copper Paddle-Wheel Metal-Organic Frameworks
2019
The structural instability in a humid environment of the majority of metal-organic frameworks (MOFs) is a challenging obstacle for their industrial-scale development. Recently, two water-resistant MOFs have been synthetized, STAM-1 and STAM-17-OEt. They both contain copper paddle wheels, like the well-known water-sensitive HKUST-1, but different organic linkers. The crystal lattice of both the MOFs undergoes a phase transition upon interaction with water molecules. Their unusual flexibility allows the controlled breaking of some interpaddle wheel Cu-O interactions in the so-called crumple zones, with a mechanism called hemilability, which is considered to have a crucial role for the stabili…
Ligand engineering in Cu(ii) paddle wheel metal–organic frameworks for enhanced semiconductivity
2020
We report the electronic structure of two metal-organic frameworks (MOFs) with copper paddle wheel nodes connected by a N2(C2H4)3 (DABCO) ligand with accessible nitrogen lone pairs. The coordination is predicted, from first-principles density functional theory, to enable electronic pathways that could facilitate charge carrier mobility. Calculated frontier crystal orbitals indicate extended electronic communication in DMOF-1, but not in MOF-649. This feature is confirmed by bandstructure calculations and effective masses of the valence band egde. We explain the origin of the frontier orbitals of both MOFs based on the energy and symmetry alignment of the underlying building blocks. The effe…