Stabilization of Pd(iii) states in nano-wire coordination complexes

Abstract

In spite of a long history of quasi-one-dimensional halogen-bridged complexes (MX-chains), all Pt and Pd complexes form the charge-density wave (CDW) state (-X...M(II)...X-M(IV)-X...), while all Ni complexes form Mott-Hubbard (MH) states (-X-Ni(III)-X-Ni(III)-X-), without exception. We have succeeded in stabilizing the Pd(iii) MH state for the first time by utilizing the following two methods: partial substitution with Ni(iii) ions, [Ni(1-x)Pd(x)(chxn)(2)Br]Br(2), and chemical pressure via long alkyl chains introduced as counter-anions, [Pd(en)(2)Br](C(n)-Y)(2).H(2)O. In both systems, it has been revealed that the electronic state of bromo-bridged Pd compounds are determined by the PdPd distances, in other words, CDW and MH states are stabilized when PdPd distances are longer and shorter than 5.26 A, respectively.