ABSTRACT
The synthesis of a structurally new type of conjugated macrocyclic ligand (1) is reported that comprises a dehydroannulene framework incorporating two 2,2'-bipyridine units. Modeling studies showed the ligand to possess an unusual chirally twisted and relatively rigid architecture capable of binding metal ions in an enforced tetrahedral coordination geometry. The macrocycle was prepared in seven steps from (2-bromophenylethynyl)-trimethylsilane (2) and characterized by spectroscopic techniques. The pyridine H3 protons in the 1H NMR spectrum of 1 showed a marked temperature dependencey that may be related to conformational opening and closing motions of the macrocyclic ring. Ligand 1 was found to spectroscopically detect the presence of Co2+, Ni2+, Cu2+, and Zn2+ and, in particular, to function as a multiple readout sensor, giving different sequences of signal output depending upon the type of metal ion analyte with which the system was addressed. Macrocycle 1 also gave a highly characteristic and specific visual output response in the presence of Zn2+ consisting of a bright turquoise fluorescence and in this respect may find applications in the sensing of this biologically important metal ion.
ABSTRACT
Ligand 3 has been shown to self-assemble under coordination of copper(II) cations in a 1:1 ratio in acetonitrile to give equilibrating mixtures of a [2 x 2] grid-type tetranuclear structure 1 and a hexanuclear achitecture of hexagonal shape 2. The latter was confirmed by determination of the crystal structure which further indicated that 2 contained acetonitrile molecules and hydroxo groups bound to the copper(II) centers, which are therefore five-coordinate. The structures assigned to 1 and 2 were further supported by the spectral (mass, UV/Vis) data. The self-assembly process is strongly dependent on the conditions of the medium. An increase in concentration in acetronitrile increases the relative amount of hexamer 2, which appears to be the favored entity at the highest concentrations that can be reached before precipitation occurs. On the other hand, in nitromethane only the tetranuclear complex 1 was detected by mass spectrometry. Replacement of nitromethane by acetonitrile and vice versa indicated the reversible switching between a solution containing either 1 alone or an equilibrium mixture of 1 and 2, respectively. In conclusion, the system described presents several remarkable features: 1) self-assembly with substrate binding, 2) dynamic combinatorial structure generation, and 3) environment-induced structural switching amounting in effect to a process of adaptive self-assembly.
ABSTRACT
Coordination of the pentatopic ligand 3 with AgI leads to the simultaneous self-assembly of two polynuclear architectures: a [4 x 5] grid-type species 10 and a quadruple-helicate 11, which contain twenty and ten silver ions. respectively. Their structures have been established by X-ray diffraction analysis of the crystals obtained as a mixture on crystallisation. Complex 10 contains two [2 x 5]-AgI10 rectangular subgrids located on opposite sides of an array of parallel ligands of 3 that are twisted into a transoid N=C-C=N arrangement around the central C-C bond; it may thus be formulated as a grid of grids: [2 x (2 x 5)]. Complex 11 is an inorganic quadruple helicate that consists of two sets of two parallel ligands of 3 connected by an array of ten silver ions. Both compounds 10 and 11 are novel types of polynuclear complexes that are composed of two subunits. Their formation points to the possibility of generating specific arrays of metal ions by self-assembly, involving, in particular, a combination of subunits within the overall entity. They represent organised patterns of ion dots of special significance in view of their formal relationship to quantum dots.
