Photochemical Structural Transformation of a Linear 1D Coordination Polymer Impacts the Electrical Conductivity

Abstract

A pair of 4-(1-naphthylvinyl)pyridine (4-nvp) ligands has been successfully aligned in head-to-tail fashion in a one-dimensional (1D) double chain ladder polymer [Cd(adc)(4-nvp)(HO)] (1; Hadc = acetylenedicarboxylic acid) that undergoes a photochemical [2 + 2] cycloaddition reaction accompanied by single-crystal to single-crystal (SCSC) structural transformation from a 1D chain to a 2D layer structure. These structural changes have a significant impact on the conductivity and Schottky nature of the compound.

Spin-crossover modulation via single-crystal to single-crystal photochemical [2 + 2] reaction in Hofmann-type frameworks

“…The stereoselective photodimerization of olefins can proceed in the solid-state if the reactive CC bonds are parallel and separated by less than 4.2 Å 12,13. This results in the modulation of physical properties, such as magnetism,14–17 photoluminescence,18 and conductivity,19,20 which has been previously reported.…”

Reversible on-off switching of spin-crossover behavior via photochemical [2+2] cycloaddition reaction

“…Due to the structural flexibility and diversity of CPs, a preorganization of the alignment of C=C bonds could be easily obtained through crystal engineering, thus giving the stereo-and regio-control of cycloaddition product through singlecrystal-to-single-crystal (SCSC) transformation [4,5]. Moreover, the opportunity to modify bulk physical properties of CPs through the change of molecular structure re-sulting from photochemical [2+2] cycloaddition reaction shows the potential in designing advanced multifunctional materials [6][7][8][9][10][11][12]. Therefore, modulation of fluorescence [6,7], conductivity [8,9], and magnetism [10][11][12] have been reported in CPs that undergo [2+2] cycloaddition.…”

“…Moreover, the opportunity to modify bulk physical properties of CPs through the change of molecular structure re-sulting from photochemical [2+2] cycloaddition reaction shows the potential in designing advanced multifunctional materials [6][7][8][9][10][11][12]. Therefore, modulation of fluorescence [6,7], conductivity [8,9], and magnetism [10][11][12] have been reported in CPs that undergo [2+2] cycloaddition. However, in most cases, only the unidirectional photochemical [2+2] cycloaddition reaction is reported.…”

Fabrication of a Zn(II)‐Based 2D Pillar Bilayer Metal‐Organic Framework for Antimicrobial Activity

“…In addition, dimensionality of the MOFs can be amplified by introducing secondary interactions. Recently, our group has designed a number of MOFs which undergo various secondary interactions to generate higher dimensional supramolecular aggregates for semiconductor applications …”