Orthogonal Grade-Separated Nanowiring of Molecular Single Chains

Quasi-one-dimensional (1D) compounds are suitable models
to develop
future nanodevices. The critical issue is that most of the several
hundred reported 1D compounds adopt parallel arrangements. Here, we
report the first example of an orthogonal grade-separated arrangement
of the halogen-bridged metal complex (MX-Chain) [PtII(en)2][PtIVCl2(en)2][FeIIICl5]2, abbreviated as [Pt(en)2Cl][FeIIICl5] (en = ethylenediamine), which is the first
example of that arrangement of molecular single chains. The space
group and topology are coincidentally same as alchemists’ gold,
Hg3−δAsF6, which aligns as atomic
single chains. This molecular nanostructure is very rare and valuable
as a three-dimensional (3D) nanowiring model. The hydrogen bond network
found in [Pt(en)2Cl][FeIIICl5] represents
a new strategy for making such nanostructures. The structural and
optical relationships are similar to those of typical Pt(II)/Pt(IV)
mixed valent MX-Chains in charge-density-wave (CDW) states. Polarized
Raman spectra strongly supported the presence of orthogonal grade-separated
chains in CDW states. Thus, this work proved the concept of molecular
single-chain grade-separated nanowiring.