NDLI: Synthesis, crystal structure, spectroscopic and electrochemical properties, and $H_{2}-evolving$ activity of a new $[PtCl(terpyridine)]^{+}$ derivative with viologen-like redox properties

Content Provider	World Health Organization (WHO)-Global Index Medicus
Author	Kobayashi, Masayuki Masaoka, Shigeyuki Sakai, Ken
Description	Author Affiliation: Kobayashi M ( Department of Chemistry, Faculty of Science, Kyushu University, Hakozaki 6-10-1, Fukuoka 812-8581, Japan.)
Abstract	A new Pt(II)-based metalloviologen analog, $[PtCl(Mepytpy)]^{2+}$ (abbreviated as $PV^{2+};$ $Mepytpy^{+}$ = 4′-(4-methyl-pyridinio)-2,2′:6′,2′′-terpyridine), was synthesized and its spectroscopic and electrochemical properties were investigated. The structures of $Mepytpy^{+}$ and $PV^{2+}$ were solved by single-crystal X-ray diffraction analysis. Electrochemical studies in DMF ( N, N-dimethylformamide ) revealed that both the first and second reduction potentials of $PV^{2+}$ $(E^{1}_{1/2}$ = −0.87 V vs. $Fc/Fc^{+}$ for $PV^{2+}/PV^{+}˙;$ $E^{2}_{1/2}$ = −1.31 V vs. $Fc/Fc^{+}$ for $PV^{+}˙/PV^{0})$ are nearly consistent with those of methylviologen (N,N′-dimetyl-4,4′-bipyridinium, $MV^{2+})$ $(E^{1}_{1/2}$ = −0.90 V vs. $Fc/Fc^{+}$ for $MV^{2+}/MV^{+}˙;$ $E^{2}_{1/2}$ = −1.28 V vs. $Fc/Fc^{+}$ for $MV^{+}˙/MV^{0}),$ where the first reduction of $PV^{2+}$ is assigned as the reduction at the $Mepytpy^{+}$ ligand bound to the Pt(II) ion. Upon the addition of a reducing agent $Na_{2}S_{2}O_{4}$ into an aqueous acetate buffer solution (pH = 5.0) of $PV^{2+},$ the generation of one-electron-reduced radical species $(PV^{+}˙)$ was spectrophotometrically observed and was assigned based on the time-dependent density functional theory (TD-DFT) calculations. The $H_{2}-evolving$ activity of $PV^{2+}$ was evaluated in the presence of a sacrificial electron donor (EDTA) in an aqueous acetate buffer solution (pH = 5.0). It was found that the stability of the metalloviologen $PV^{2+}$ during the photolysis is much higher than that of the parent compound $[PtCl(tpy)]^{+}.$
ISSN	14779226
Issue Number	16
Journal	Dalton Trans.
Volume Number	41
e-ISSN	13645447
Language	English
Publisher	Royal Society of Chemistry
Publisher Date	2012-04-28
Publisher Place	Great Britain (UK)
Access Restriction	Subscribed
Subject Keyword	Chemistry
Content Type	Text
Resource Type	Article
Subject	Inorganic Chemistry

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