Australian Journal of Chemistry Australian Journal of Chemistry Society
An international journal for chemical science
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Structural, Spectroscopic, and Electrochemical Characterization of Semi-Conducting, Solvated [Pt(NH3)4](TCNQ)2·(DMF)2 and Non-Solvated [Pt(NH3)4](TCNQ)2

Jinzhen Lu A G , Ayman Nafady A B G , Brendan F. Abrahams C , Muhammad Abdulhamid A D , Bjorn Winther-Jensen E F , Alan M. Bond A H and Lisandra L. Martin A H
+ Author Affiliations
- Author Affiliations

A School of Chemistry, Monash University, Clayton, Vic. 3800, Australia.

B Current address: Chemistry Department, College of Science, King Saud University, Riyadh 11451, Saudi Arabia.

C School of Chemistry, University of Melbourne, Melbourne, Vic. 3010, Australia.

D Current address: Department of Applied Physics, Chalmers University of Technology, Göteborg SE-412 96, Sweden.

E Materials Engineering, Monash University, Clayton, Vic. 3800, Australia.

F Current address: Department of Advanced Science and Engineering, Waseda University, Tokyo 169-8555, Japan.

G Joint first authors with an equal contribution.

H Corresponding authors. Email: alan.bond@monash.edu; lisa.martin@monash.edu

Australian Journal of Chemistry 70(9) 997-1005 https://doi.org/10.1071/CH17245
Submitted: 7 May 2017  Accepted: 16 June 2017   Published: 2 August 2017

Abstract

The demand for catalysts that are highly active and stable for electron-transfer reactions has been boosted by the discovery that [Pt(NH3)4](TCNQF4)2 (TCNQF4 = 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane) is an efficient catalyst. In this work, we prepare and characterize the two related [Pt(NH3)4]2+ complexes, [Pt(NH3)4](TCNQ)2·(DMF)2 (1) and [Pt(NH3)4](TCNQ)2 (2). Reaction of [Pt(NH3)4](NO3)2 with LiTCNQ in a mixed solvent (methanol/dimethylformamide, 4 : 1 v/v) gives [Pt(NH3)4](TCNQ)2·(DMF)2 (1), whereas the same reaction in water affords [Pt(NH3)4](TCNQ)2 (2). 2 has been previously reported. Both 1 and 2 have now been characterized by single-crystal X-ray crystallography, Fourier-transform (FT)IR, Raman and UV-vis spectroscopy, and electrochemistry. Structurally, in 1, the TCNQ1- anions form infinite stacks with a separation between adjacent anions within the stack alternating between 3.12 and 3.42 Å. The solvated structure 1 differs from the non-solvated form 2 in that pairs of TCNQ1- anions are clearly displaced from each other. The conductivities of pressed pellets of 1 and 2 are both in the semi-conducting range at room temperature. 2 can be electrochemically synthesized by reduction of a TCNQ-modified electrode in contact with an aqueous solution of [Pt(NH3)4](NO3)2 via a nucleation growth mechanism. Interestingly, we discovered that 1 and 2 are not catalysts for the ferricyanide and thiosulfate reaction. Li+ and tetraalkylammonium salts of TCNQ1-/2- and TCNQF41-/2- were tested for potential catalytic activity towards ferricyanide and thiosulfate. Only TCNQF41-/2- salts were active, suggesting that the dianion redox level needs to be accessible for efficient catalytic activity and explaining why 1 and 2 are not good catalysts. Importantly, the origin of the catalytic activity of the highly active [Pt(NH3)4](TCNQF4)2 catalyst is now understood, enabling other families of catalysts to be developed for important electron-transfer reactions.


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