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Chemistry. 2013 Sep 9;19(37):12325-35. doi: 10.1002/chem.201300865. Epub 2013 Jul 29.

Charge-transfer solids using nucleobases: supramolecular architectures composed of cytosine and [Ni(dmit)2] assembled by multiple hydrogen bonds and heteroatomic contacts.

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Faculty of Agriculture, Meijo University, Shiogamaguchi 1-501 Tempaku-ku, Nagoya 468-8502 (Japan), Fax: (+81) 52-833-7200.


Protonated species of the nucleobase cytosine (C), namely the monoprotonated CH(+) and the hemiprotonated CHC(+), were used to obtain four charge-transfer complexes of [Ni(dmit)2] (dmit: 1,3-dithiole-2-thione-4,5-dithiolate). Diffusion methods afforded two semiconducting [Ni(dmit)2](-) salts; (CH)[Ni(dmit)2](CH3CN) (1) and (CHC)[Ni(dmit)2] (2). In salt 1, the [Ni(dmit)2](-) ions with a S = 1/2 spin construct a uniform one-dimensional array along the molecular long axis, and the significant intermolecular interaction along the face-to-face direction results in a spin-singlet ground state. In contrast, salt 2 exhibits the Mott insulating behavior associated with uniform 1D arrays of [Ni(dmit)2](-), which assemble a two-dimensional layer that is sandwiched between the layers of hydrogen-bonded CHC(+) ribbons. Multiple hydrogen bonds between CHC(+) and [Ni(dmit)2](-) seem to result in the absence of structural phase transition down to 0.5 K. Electrooxidation of [Ni(dmit)2](-) afforded the polymorphs of the [Ni(dmit)2](0.5-) salts, (CHC(+))[{Ni(dmit)2}(0.5-)]2 (3 and 4), which are the first mixed-valence salts of nucleobase cations with metal complex anions. Similar to 2, salt 3 contains CHC(+) ribbons that are sandwiched between the 2D [Ni(dmit)2](0.5-) layers. In the layer, the [Ni(dmit)2](0.5-) ions form dimers with a S = 1/2 spin and the narrow electronic bandwidth causes a semiconducting behavior. In salt 4, the CHC(+) units form an unprecedented corrugated 2D sheet, which is sandwiched between the 2D [Ni(dmit)2](0.5-) layers that involve ring-over-atom and spanning overlaps. In contrast to 3, salt 4 exhibits metallic behavior down to 1.8 K, associated with a wide bandwidth and a 2D Fermi surface. The ability of hydrogen-bonded CHC(+) sheets as a template for the anion radical arrangements is demonstrated.


conducting materials; crystal engineering; hydrogen bonds; magnetic properties; nucleobases

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