1.Soluble heterometallic coordination polymers based on a bis-terpyridine-functionalized dioxocyclam ligand.
Gasnier A1, Barbe JM, Bucher C, Duboc C, Moutet JC, Saint-Aman E, Terech P, Royal G. Inorg Chem. 2010 Mar 15;49(6):2592-9. doi: 10.1021/ic901832q.
Soluble homo- and heterometallic coordination polymers containing transition metal cations (Cu(2+), Fe(2+), Co(2+), and Ni(2+) ions) were prepared in a two-step procedure using a polytopic bis(terpyridine)dioxocyclam ligand 1H(2) (dioxocyclam = 1,4,8,11-tetraazacyclotetradecane-5,7-dione). These supramolecular systems incorporate two different metal complexes, the metal cations being located both between two terpyridine units and in the macrocyclic framework. The characterization of these soluble architectures was investigated by cyclic voltammetry, mass spectrometry, viscosimetry, and UV-vis absorption and electron paramagnetic resonance (EPR) spectroscopies. Our results clearly indicate the formation of well-organized heterometallic polymers in which two different metal ions alternate in the self-assembled structure. These investigations furthermore brought to light an original acid-controlled disassembling process of the homometallic copper(II) polymer into dinuclear complexes.
Mashuta MS1, Pimenov KV, Grapperhaus CA. Acta Crystallogr C. 2002 Apr;58(Pt 4):O226-7. Epub 2002 Mar 21.
Molecules of 1,4,8,11-tetraazacyclotetradecane-5,7-dione, or cis-dioxocyclam, C(10)H(20)N(4)O(2), lie across mirror planes in space group Cmca; the crystal structure reveals interleaved columns of cis-dioxocyclam molecules along the 2(1) screw axis parallel to the crystallographic b axis. The columns are interconnected in a chain-like arrangement by an amido hydrogen-bonding network (N* * *O = 2.816 A) and an amino hydrogen-bonding network (N* * *N = 3.193 A). The intracolumn spacing is 9.02 A.
3.Labeling and in vivo evaluation of novel copper(II) dioxotetraazamacrocyclic complexes.
Cutler CS1, Wuest M, Anderson CJ, Reichert DE, Sun Y, Martell AE, Welch MJ. Nucl Med Biol. 2000 May;27(4):375-80.
64Cu shows promise as both a positron emission tomography imaging and radiotherapeutic radionuclide due to its half-life (T(1/2) = 12. 7 h), decay characteristics (beta(+) [19%]; beta(-) [40%]), and the capability to produce it on a large-scale with high specific activity on a biomedical cyclotron. Macrocyclic chelators are generally used as bifunctional chelators to attach Cu(II) to antibodies and peptides due to their relatively high in vitro stability. To investigate neutral Cu(II) complexes, we performed labeling experiments with six tetraazamacrocyclic ligands with different chelate ring sizes. 1,4,8,11-Tetraazacyclotetradecane-3, 9-dione (1), 1,4,8,11-tetraazacyclotetradecane-5,7-dione (2), 1,4,7, 10-tetraazacyclotridecane-11,13-dione (3), 1,4,7, 10-tetraazacyclotridecane-2,9-dione (4), 1,4,7, 10-tetraazacyclododecane-2,9-dione (5), and 1,4,7, 10-tetraazacyclotridecane-3,8-dione (6) were radiolabeled with (64)Cu. Only (64)Cu-labeled 1 readily formed a complex in high purity, and therefore was evaluated in vivo.
4.Syntheses, solid state and solution structures of the palladium(II) complexes of malonamide-derived open-chain and macrocyclic ligands.
Gavrish SP1, Lampeka YD, Pritzkow H, Lightfoot P. Dalton Trans. 2010 Sep 7;39(33):7706-13. doi: 10.1039/c0dt00376j. Epub 2010 Jul 23.
The crystal structures of the palladium(II) complexes of the open-chain and macrocyclic ligands PdL(1).3H(2)O, PdL(2).6H(2)O and PdL(3).5H(2)O have been determined (H(2)L(1) = 1,4,8,11-tetraazaundecane-5,7-dione, H(2)L(2) = 1,4,8,11-tetraazacyclotetradecane-5,7-dione, H(2)L(3) = 1,4,8,11-tetraazacyclotridecane-5,7-dione). The coordination polyhedra of the palladium(II) ions in all complexes are formed by two deprotonated amide and two amine donors with Pd-N distances being similar in PdL(1) and PdL(2) and substantially shorter in PdL(3). A detailed analysis of the (1)H NMR spectra of the macrocyclic complexes supports the formation in aqueous solution of only N-meso isomers of both compounds in agreement with the X-ray data. The spectra of the palladium(II) macrocyclic complexes are shifted downfield as a whole as compared to those of the nickel(II) analogues with the shifts being essentially non-uniform. The latter feature can be related to the differences in magnetic anisotropy of the M-N bonds.