Ab Initio Study of Phosphorescence of Hetero[8]Circulenes

  • R. R. ValievEmail author
  • G. V. Baryshnikov
  • V. N. Cerepanov
  • D. Sundholm

Quantum chemical calculations of phosphorescence lifetime are performed for the first time by ab initio CC2 and TD-DFT methods for hetero[8]circulenes bearing Si and Ge atoms. According to the results of calculations, a lower value of τphos for tetragermatetrathia[8]circulene (II) originates from two factors: almost 29 times more distorted main macrocycle II and almost four times larger spin-orbit coupling matrix element between T1 and S0 by virtue of heavier Ge atoms as compared to Si. The τphos values calculated by CC2 ideally agree with its experimental value; the difference is less than 2 and 0.3 s for tetrasilatetrathia[8]circulene (I) and tetragermatetrathia[8]circulene (II) molecules, respectively. The agreement of the lifetimes calculated by TD-DFT is only within an order of magnitude. The main intramolecular decay channel of the T1 state is internal conversion between T1 and S0 owing to simultaneous spin-orbit and nonadiabatic interaction of their wavefunctions.


circulenes hetero[8]circulenes oxygen quantum chemistry photodynamic therapy phosphorescence 


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© Springer Science+Business Media, LLC, part of Springer Nature 2019

Authors and Affiliations

  • R. R. Valiev
    • 1
    • 2
    Email author
  • G. V. Baryshnikov
    • 1
  • V. N. Cerepanov
    • 1
  • D. Sundholm
    • 3
  1. 1.National Research Tomsk State UniversityTomskRussia
  2. 2.National Research Tomsk Polytechnic UniversityTomskRussia
  3. 3.University of HelsinkiHelsinkiFinland

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