Abstract
Abstract The surface adsorption structures of two Schiff-base metal complexes, [N,N′-bis(5-octylsalicylidene)-o-phenylenediaminato]nickel(II) (1) and [N,N′-bis(3,5-dioctylsalicylidene)-o-phenylenediaminato]nickel(II) (2), are imaged using scanning tunneling microscopy (STM), and compared with the dimeric structure predicted by single-crystal X-ray diffraction and NMR analyses. STM images of 1 and 2 obtained at an o-dichlorobenzene/HOPG interface showed that 1 was adsorbed in the form of dimers, while 2 was adsorbed as monomers at HOPG surface. The surface structure of 1 was similar to that of the reported salen complex analogue. 1H NMR measurement revealed that the equilibrium constants of dimer formation for 1 and 2 in chloroform-d were determined to be K (= [dimer]/[monomer]2) = 14.5 and 1.9 mol−1 dm3, respectively. This decreased tendency of 2 to form dimer is concluded to be the reason why 2 did not form dimers at HOPG surface. The crystal structure of 1 in which 1 is found to form dimers is also presented.
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