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|標題:||Probing the electronic communication of linear heptanickel and nonanickel string complexes by utilizing two redox-active Ni-2(napy)(4) (3+) moieties||作者:||Hua, S.A.
|關鍵字:||metal-metal interactions;theoretical-analysis;quantum-mechanics;magnetic-properties;new-generation;ligands;conductance;chains;wires;atoms||Project:||Dalton Transactions||期刊/報告no：:||Dalton Transactions, Volume 39, Issue 16, Page(s) 3890-3896.||摘要:||
Two extended nickel string complexes, [Ni-7(bnapy)(4)Cl-2](Cl) 2 (2) and [Ni-9(bnapya)(4)Cl-2](PF6)(2) (3) (bnapy(2-) = 2,6-bis(1,8-naphthyridylamido)pyridine and bnapya(3-) = bis(6-(1,8-naphthyridylamido)pyridyl)amido),which possess two redox-active [Ni-2(napy)(4)](3+) units, were synthesized and characterized. The electronic communication between the two redox-active units in both complexes can be investigated not only by magnetic measurements but also by analyzing the difference between two consecutive one-electron oxidation peaks (Delta E-1/2) of 2 and 3. The antiferromagnetic coupling between the two [Ni-2(napy)(4)](3+) fragments become weaker as the metal frameworks are elongated (J = -13.21 and -1.48 cm(-1) for 2 and 3, respectively). Moreover, the Delta E-1/2 values of 2 and 3 are 110 and 84 mV, respectively, which are smaller than that (300 mV) of their pentanickel analogue [Ni-5(bna)(4)(Cl)(2)](PF6)(2) (bna(-) = bisnaphthyridylamido) ( 1). These Delta E-1/2 values indicate that the electronic communication decreases with increasing number of inner diamagnetic nickel ions in nickel string complexes.
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