Premium
Solid–Gas Phase Synthesis of Coordination Networks by Using Redox‐Active Ligands and Elucidation of Their Oxidation Reaction
Author(s) -
Den Taizen,
Usov Pavel M.,
Kim Jaejun,
Hashizume Daisuke,
Ohtsu Hiroyoshi,
Kawano Masaki
Publication year - 2019
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201902105
Subject(s) - redox , chemistry , solid phase synthesis , gas phase , combinatorial chemistry , phase (matter) , oxidation reduction , inorganic chemistry , organic chemistry , biochemistry , peptide
Formation of coordination networks is a complex process affected by a multitude of factors. Many synthetic strategies have been developed that attempt to control these factors and direct the structure of the final product. Coordination bond formation and structural assembly processes, however, typically take place either in the solution or solid states. In comparison, gas‐phase network synthesis remains largely unexplored. Herein, two new two‐dimensional coordination networks are obtained from the solid–gas phase reaction between ZnX 2 (X=I, Br) and the redox‐active 2,5,8‐tri(4‐pyridyl)1,3‐diazaphenalene (HTPDAP) ligand. Their structures were solved by ab initio powder X‐ray diffraction analysis and feature a novel Zn halide trimeric cluster. This strategy is contrasted with a conventional solvothermal synthesis, which led to a one‐dimensional coordination polymer instead. The intrinsic electroactive properties of these materials were probed by solid‐state cyclic voltammetry measurements, which revealed the presence of HTPDAP and halide‐based processes. Chemical oxidation of the two‐dimensional networks by using NOPF 6 agent, unexpectedly, led to the formation of a nitrated analog of HTPDAP, the PF 6 − salt of diprotonated 4,6,7,9‐tetranitro‐2,5,8‐tris(4‐pyridyl)diazaphenalene cation (denoted N ‐TPDAP), which was isolated and characterized. These results provide deeper insights into the oxidation process of HTPDAP‐containing networks and uncover unique redox‐induced chemical transformations.