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Electrochemical and Chemical Synthesis of [ZnTCNQF 4 (DMF) 2 ] · 2DMF – A 2D Network Coordination Polymer
Author(s) -
Tran Manh D.,
Lu Jinzhen,
Mai Bay V.,
Vo Nguyen T.,
Le Hai T.,
Bond Alan M.,
Martin Lisandra L.
Publication year - 2019
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201900431
Subject(s) - chemistry , electrochemistry , acetonitrile , cyclic voltammetry , inorganic chemistry , infrared spectroscopy , coordination polymer , molecule , dimethylformamide , solvent , crystal structure , crystallography , electrode , organic chemistry
The synthesis of the 2D network coordination polymer (CP) [ZnTCNQF 4 (DMF) 2 ] · 2DMF by electrochemical and chemical approaches is reported. The electrochemistry of TCNQF 4 (TCNQF 4 = 2,3,5,6‐tetrafluoro‐7,7,8,8‐tetracyanoquinodimethane) in the presence of 0.1 M Zn 2+ (as the perchlorate salt) in an MeCN/DMF (MeCN = acetonitrile; DMF = dimethylformamide) solvent mixture (5 % DMF) yields the new CP. Under conditions of cyclic voltammetry, and in the presence of Zn 2+ , the TCNQF 4 1–/2– diffusion controlled reduction process is replaced by a surface‐based reaction derived from the title compound being formed on the electrode surface. This material also was prepared by the addition of a Zn 2+ solution (DMF) to a TCNQF 4 2– solution (MeCN) prepared by bulk reductive electrolysis of neutral TCNQF 4 . Alternatively, reaction of Zn(ClO 4 ) 2 in DMF with Li 2 TCNQF 4 in MeOH forms colourless, highly crystalline material. Characterisation by infrared spectroscopy (IR) and X‐ray powder diffraction (XPD) confirmed that both chemical and electrochemical methods gave the same material, although only the chemical method afforded single crystals suitable for X‐ray structural analysis. X‐ray crystallography and elemental analysis confirmed the empirical formula as [ZnTCNQF 4 (DMF) 2 ] · 2DMF in which two DMF molecules are coordinated to the central zinc ion and the remaining two are present as solvates within the lattice. Analysis by IR, UV/Vis and electrochemical methods confirmed that only TCNQF 4 2– was present upon dissolution of either material in DMF. Density functional theory (DFT) calculations, which compare well with the experimental IR spectrum were used to assist with the assignment of the major IR bands.