Orthogonal Grade-Separated Nanowiring of Molecular Single Chains

Abstract

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) [Pt II (en) 2 ][Pt IV Cl 2 (en) 2 ][Fe III Cl 5 ] 2 , abbreviated as [Pt(en) 2 Cl][Fe III Cl 5 ] (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, Hg 3−δ AsF 6 , 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) 2 Cl][Fe III Cl 5 ] 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.

Solvent-Mediated Separation and Reversible Transformation of 1D Supramolecular Polymorphs Built from [W10O32]4– Templated 48-Nuclei Silver(I) Cluster

“…All these changes working together enable the packing alignment of 1D supramolecular chains varying from a parallel ( Ag48T ) to staggered ( Ag48M ) pattern, which is a rare but useful arrangement in molecular single chains (Figure ). Based on the currently available data, a plausible mechanism was proposed and discussed in detail, as shown in Scheme S2.…”

Hexagonal crystalline Magnus’ green salt analogues prepared from hydroxy-functionalised Pt and Pd complexes

“…The grade separation of molecular single chains is a quite rare arrangement in molecular crystals. Recently, we found other examples: an orthogonally grade-separated 1D MX-type chain complex induced by a hydrogen-bond network among the chains and counteranions, 25 and trigonal grade separation in 1D coordination polymers induced by helical π-stacking interaction between π-conjugated cores. 26 The origin of the unusual trigonal grade separation in 1 and 2 is discussed later.…”