Research output: Contribution to journal › Article › peer-review
Excitation wavelength dependent emission of silver(i) complexes with a pyrimidine ligand. / Shekhovtsov, Nikita A.; Vinogradova, Katerina A.; Berezin, Alexei S. et al.
In: Inorganic Chemistry Frontiers, Vol. 7, No. 11, 07.06.2020, p. 2212-2223.Research output: Contribution to journal › Article › peer-review
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TY - JOUR
T1 - Excitation wavelength dependent emission of silver(i) complexes with a pyrimidine ligand
AU - Shekhovtsov, Nikita A.
AU - Vinogradova, Katerina A.
AU - Berezin, Alexei S.
AU - Sukhikh, Taisiya S.
AU - Krivopalov, Viktor P.
AU - Nikolaenkova, Elena B.
AU - Bushuev, Mark B.
PY - 2020/6/7
Y1 - 2020/6/7
N2 - 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.
AB - 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.
KW - DOUBLE-PROTON-TRANSFER
KW - GRAPHENE QUANTUM DOTS
KW - DIPOLAR MOLECULES
KW - FLUORESCENCE
KW - PHOTOLUMINESCENCE
KW - TEMPERATURE
KW - DERIVATIVES
KW - POLYMERS
KW - 2-AMINOPYRIMIDINE
KW - COPPER(I)
UR - http://www.scopus.com/inward/record.url?scp=85090774757&partnerID=8YFLogxK
U2 - 10.1039/d0qi00254b
DO - 10.1039/d0qi00254b
M3 - Article
AN - SCOPUS:85090774757
VL - 7
SP - 2212
EP - 2223
JO - Inorganic Chemistry Frontiers
JF - Inorganic Chemistry Frontiers
SN - 2052-1545
IS - 11
ER -
ID: 25644411