Excitation wavelength dependent emission of silver(i) complexes with a pyrimidine ligand

Nikita A. Shekhovtsov, Katerina A. Vinogradova, Alexei S. Berezin, Taisiya S. Sukhikh, Viktor P. Krivopalov, Elena B. Nikolaenkova, Mark B. Bushuev

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5 Citations (Scopus)

Abstract

Silver(i) complexes with 2-amino-4-phenyl-6-methylpyrimidine (L), [Ag3L2(H2O)0.55(NO3)3]n (1) and [Ag2L2(PPh3)2(NO3)2] (2), have been synthesized and structurally characterized. In the solid state the free ligand L demonstrates dual fluorescence: a high energy band at 375 nm is the emission of the monomer L while a low-energy band at 450 nm can be attributed to the emission of the tautomeric dimer, L2-imino, formed in the excited state double proton transfer (ESDPT) process. In the solid state the complexes demonstrate excitation wavelength dependent photoluminescence originating from three emission mechanisms (hereafter abbreviated as A, B and C for complex 1; A′, B′ and C′ for complex 2). The spectroscopic and computational results reveal that these emission mechanisms can be assigned to metal + nitrate anion to ligand L charge transfer phosphorescence (mechanisms A and A′), excimer 1π-π∗ fluorescence (mechanism B), fluorescence of L2-imino dimeric units formed due to ESDPT (mechanism B′) and ligand-centered 1π-π∗/1n-π∗ fluorescence (mechanisms C and C′). The luminescence of complex 1 at λex = 340 nm shows thermochromic behavior; the emission color dramatically changes from blue-green at 77 K to yellowish green at 175 K and white at 300 K.

Original languageEnglish
Pages (from-to)2212-2223
Number of pages12
JournalInorganic Chemistry Frontiers
Volume7
Issue number11
DOIs
Publication statusPublished - 7 Jun 2020

Keywords

  • DOUBLE-PROTON-TRANSFER
  • GRAPHENE QUANTUM DOTS
  • DIPOLAR MOLECULES
  • FLUORESCENCE
  • PHOTOLUMINESCENCE
  • TEMPERATURE
  • DERIVATIVES
  • POLYMERS
  • 2-AMINOPYRIMIDINE
  • COPPER(I)

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