A dodecanuclear 3 × [2 × 2] nickel(II) complex has been obtained via the self-association of three tetranuclear [2 × 2] molecular grids. X-ray diffraction shows a "propeller-like" structure of the [Ni(4)](3) scaffold with a central μ(3)-hydroxide. The dodecanuclear species remains stable in solution and can be deposited without decomposition on highly ordered pyrolytic graphite surfaces.

The reaction of 2H-benzotriazole (1) with dichloroacetic acid leads to the symmetric bis(2H-benzotriazol-2-yl)methane (2c) in 40 % yield. Deprotonation of 2c at the bridging methylene group and subsequent carboxylation with CO 2 yielded the new tripodal N,N,O ligand bis(2H-benzotriazol-2-yl)acetic acid Hbbta (3). The sterically less demanding sodium 3,3-bis(1H-1,2,4-triazol-1-yl)propionate Na[btp] (5) was obtained by saponification of methyl 3,3-bis(1H-1,2,4-triazol-1-yl)propionate (4). The heteroscorpionate ligand 3 was treated with [MnBr(CO) 5 ] and [RuCl 2 (PPh 3 ) 3 ] to form the manganese tricarbonyl complex [Mn(bbta)(CO) 3 ] (6) and the air stable ruthenium complex [Ru(bbta)Cl(PPh 3 ) 2 ] (7). DFT calculations and the IR spectra of the carbonyl complex 6 reveal ligand 3

Novel κ(3) -N,N,O ligands tend to form 1D coordination polymer strands. Deposition of 1D structures on highly oriented pyrolytic graphite (HOPG) was achieved from diluted solutions and polymer strands have been studied on HOPG by AFM/STM. Single strands were mapped by STM and their electronic properties were subsequently characterized by current imaging tunneling spectroscopy (CITS). Periodic density functional calculations simulating a polymer strand deposited on a HOPG surface are in agreement with the zig-zag structure indicated by experimental findings. Both the observed periodicity and the Zn-Zn distances can be reproduced in the simulations. Van der Waals interactions were found to play a major role for the geometry of the isolated polymer strand, for the adsorption geometry on HOPG, as well as for the adsorption energy.