Dual emission of 2-amino-4-methylpyrimidine: A theoretical study

N. A. Shekhovtsov, K. A. Vinogradova, E. B. Nikolaenkova, V. P. Krivopalov, M. B. Bushuev

Research output: Contribution to journalArticlepeer-review

Abstract

Abstract: DFT and TD-DFT calculations at the B3LYP/LANL2DZ level of theory are performed in order to explain the origins of dual fluorescence and uncover the relaxation pathways of 2-amino-4-methylpyrimidine (L). The computations are in good agreement with experimental data. A high-energy emission band in the photoluminescence spectrum of 2-amino-4-methylpyrimidine (λ max = 350 nm) is related to the fluorescence of monomer L. Comparison of calculated and experimental IR and absorption spectra reveals that in the solid state L molecules form supramolecular {N–H···N} n hydrogen bonded associates. The formation of such associates favors the excited state double proton transfer (ESDPT). Calculated 2D potential energy curves for the ground and first singlet excited states of dimeric associates L 2 indicate the presence of two stable forms, L 2-amino and L 2-imino. The low-energy band in the emission spectrum of 2-amino-4-methylpyrimidine (λ max = 445 nm) is probably associated with the fluorescence of the L 2-imino form. Both fluorescence bands have a mixed π–π*, n–π* character as is evidenced by frontier orbitals involved in S 1–S 0 transitions.

Original languageEnglish
Pages (from-to)1521-1529
Number of pages9
JournalJournal of Structural Chemistry
Volume61
Issue number10
DOIs
Publication statusPublished - Oct 2020

Keywords

  • dual emission
  • pyrimidine
  • hydrogen bond
  • photoisomerization
  • excited state double proton transfer
  • supramolecular chemistry
  • DOUBLE-PROTON-TRANSFER
  • CRYSTAL-STRUCTURE
  • COMPLEX
  • DFT

OECD FOS+WOS

  • 1.04 CHEMICAL SCIENCES

Fingerprint

Dive into the research topics of 'Dual emission of 2-amino-4-methylpyrimidine: A theoretical study'. Together they form a unique fingerprint.

Cite this