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Pure and Applied Chemistry

The Scientific Journal of IUPAC

Ed. by Burrows, Hugh / Stohner, Jürgen

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Volume 85, Issue 7


Photoinduced charge separation in a PtII acetylide donor–acceptor triad based on 2-(1-pyrazole)-pyridine modified with naphthalene mono-imide electron acceptor

Igor V. Sazanovich / Mohammed A. H. Alamiry / Anthony J. H. M. Meijer / Michael Towrie
  • Corresponding author
  • Laser for Science Facility, Rutherford Appleton Laboratory, Oxfordshire, OX11 0QX, UK
  • Other articles by this author:
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/ E. Stephen Davies / Robert D. Bennett / Julia A. Weinstein
Published Online: 2013-06-21 | DOI: https://doi.org/10.1351/PAC-CON-13-04-02

A class of molecular electron transfer cascades—those based on PtII complexes of 2-(1-pyrazole)-pyridine (pzpy) ligands—are reported. The synthesis of a new electron-acceptor imide-modified pzpy ligands is reported, and their application to transition-metal chemistry demonstrated by the synthesis of the PtII chloride and acetylide complexes. These donor–acceptor assemblies are promising models for investigation of photoinduced charge separation. Accordingly, picosecond time-resolved infrared (TRIR) and femtosecond transient absorption (TA) studies have been undertaken to elucidate the nature and dynamics of the lowest excited states in Pt(NAP-pyr-pyrazole)(–CC–Ph–C7H15)2. It has been established that the initial population of an MLL'CT excited state in the chromophoric [Pt(pyridine-pyrazole)(acetylide)] core is followed by an electron transfer to the naphthalimide (NAP) acceptor, forming a charge-separated state. This state is characterized by a large shift in ν(CO) vibrations of the NAP acceptor, as well as by a very intense and broad [×10 times in comparison to ν(CO)] asymmetric acetylide stretch which incorporates –CC–Pt–CC– framework and occurs at approximately 300 cm–1 lower in energy than its ground-state counterpart. In CH2Cl2 at room temperature, the charge-separated state with the lifetime of 150 ps collapses into an almost isoenergetic NAP-localized triplet state; the rate of this transformation changes upon decreasing the temperature to 263 K. This final excited state, 3NAP-(pyr-pyrazole)Pt(–CC–Ph–C7H15)2, has an unusually long, for PtII complexes, excited-state lifetime of tens of microseconds. The work demonstrates the possibility of tuning excited-state properties in this new class of PtII chromophores designed for electron-transfer cascades.

Keywords: 2-(1-pyrazole)-pyridine; charge-transfer dynamics; femtosecond transient absorption spectroscopy; imides; photoinduced electron transfer; platinum acetylides; platinum diimine; solar energy; time-resolved infrared spectroscopy; ultrafast laser spectroscopy


IUPAC Symposium on Photochemistry, International Symposium on Photochemistry, PHOTO, Photochemistry, XXIVth, Coimbra, Portugal, 2012-07-15–2012-07-20


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About the article

Published Online: 2013-06-21

Published in Print: 2013-06-21

Citation Information: Pure and Applied Chemistry, Volume 85, Issue 7, Pages 1331–1348, ISSN (Online) 1365-3075, ISSN (Print) 0033-4545, DOI: https://doi.org/10.1351/PAC-CON-13-04-02.

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