Supramolecular assemblies copper

Irradiation of 1,4,8,11,15,18,22,25-octabutoxyphthalocyanine or its copper derivatives in degassed ethanol containing triethanolamine causes its reduction by a mechanism which involves a higher excited state of the substrate,and a plot of the log of the rate constants for the photoinduced intramolecular electron transfer in a supramolecular assembly of Zn and Au porphyrins bridged by diphenylphenanthroline has been found to decrease linearly with diminishing energy difference between the HOMO and LUMO of the participating orbitals. ... 

With this method, a methoxy substituted polyphenylene precursor was synthesized. The molecule was adsorbed on a copper surface and the cyclodehydrogenation was thermally induced directly on the surface [46]. The synthesis of substituted HBCs permits tuning of the properties in this class of compounds, for example in a columnar supramolecular assembly [47]. The influence of substitution at the periphery with either oligoether (water soluble) or alkyl chains with different degrees of branching and different lengths has been studied [48]. 

Sdn que O, Campion M, Douziech B, Giorgi M, Riviere E, Journaux Y, Le Mest Y, Reinaud O. Supramolecular assembly with calix[6]arene and copper ions formation of a novel tetra-nuclear core exhibiting unusual redox properties and catecholase activity. Eur J Inorg Chem 2002 8 2007-14. 

An exciting development in dithiocarbamate chemistry is the synthesis by Beer and co-workers (325,1489) of a range of supramolecular complexes containing nickel(II), zinc(II), and copper(II) bis(dithiocarbamate) centers. These include the preparation of nano-sized resorcarene-based polymetallic assemblies, copper(II) dithiocarbamate macrocycles (62,326,1469,1470), crown-ether derivatives (1471), cryptands (492), and catenanes (544). Details of this work are given in this section and also within the copper and zinc sections (Section IV.H.l and IV.I.l). 

Selenotrithionates, 2 256 Selenous acid, secondary bonding by, 15 19 Self-assembling metal complexes, 46 174-175, xee also Supramolecular copper (l)/silver (I) complexes... 

While today the construction of such bidentate phosphine ligands with the use of an assembly metal is referred to as supramolecular chemistry, this is not to say that there are no examples in older literature utilizing this principle. Actually, there are many and using as a search term hetero bimetallic complexes (a named coined in the early 1980s) leads us to a plethora of complexes. For instance in complex 29, reported by Rauchfuss in 1982, one would consider copper as the assembly metal and platinum as the potential catalytic metal [70]. 

Similarly, when a mixture of the two tris-bipyridine ligands 129 and 148 is allowed to react simultaneously with copper(l) and nickel(il) ions, only the double helicate 132 and the triple helicate 149 are formed (Figure 49). Thus, parallel operation of two programmed molecular systems leads to the clean self-assembly of two well-defined helical complexes from a mixture of their four components in a process involving the assembly of altogether 11 particles of four different types into two supramolecular species. 

Further studies on the supramolecular coordination chemistry of copper(II) focused on the synthesis of oligonuclear complexes by self-assembly with the pentadentate ligand (L3)2 with 2,6-pyridinyl-spacer [70]. To this end, H2L3 (4) was treated with calcium hydride and copper(II) acetate to give the metallocoronate [(Cac Cu2(L3)2 )(OAc)2] (5 Scheme 2). In the crystal, 5 is present as a dinuclear copper(II) coronate in which a calcium ion is encapsulated in the center two acetates act as counterions. 

The remarkable cylindrical supramolecular structure 56 forms by spontaneous assembly from 11 particles five ligand molecules (three 5,5 -linked bis-bipyridines and two hexa-azatriphenylene ligands) and six copper(I) ions. The hexa-azatri-phenylene ligands remain flat and are orientated almost parallel to each other they are not eclipsed as shown in 56 but are rotated with respect to each other by 27°. Reflecting this, the overall structure has a triple-helical twist. After allowing for van der Waals radii, the internal cavity is about 4 A in diameter and 4 A high. 

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