TY - JOUR
T1 - Synthesis, structure, Hirshfeld surface analysis and photophysical studies of red emitting europium acetylacetonate complex incorporating a phenanthroline derivative
AU - Ilmi, Rashid
AU - Kansız, Sevgi
AU - Dege, Necmi
AU - Khan, Muhammad S.
N1 - Publisher Copyright:
© 2019 Elsevier B.V.
PY - 2019/5/15
Y1 - 2019/5/15
N2 - Two new octa-coordinated red emitting complexes of the type [Ln(acac) 3 (Br 2 -phen)] [acac: acetylacetonate, Br 2 -phen: 4,7-dibromo-1,10-phenanthroline, Ln: Sm(III) and Eu(III)] have been synthesized and characterized. Single crystal X-ray diffraction (SCXD) of [Eu(acac) 3 (Br 2 -phen)] and [Eu(acac) 3 (H 2 O) 2 ](H 2 O) revealed distorted square antiprism structure for both complexes. 2D fingerprint plots and Hirshfeld surface analyses signify important interactions in crystal packing [H⋯H (72.2%), O⋯H/H⋯O (18.9%) and C⋯H/H⋯C (6.7%) contacts for [Eu(acac) 3 (H 2 O) 2 ](H 2 O), while [Eu(acac) 3 (Br 2 -phen)] showed H⋯H (40.5%), Br⋯H/H⋯Br (12.9%) and O⋯H/H⋯O (6.5%)] contacts]. Photophysical measurements gave quantum yield (Q Ln L ) of 1.1 and 13% with corresponding luminescence lifetime (τ obs ) of 38.76 ± 0.61 μs and 790 ± 1.53 μs for [Sm(acac) 3 (Br 2 -phen)] and [Eu(acac) 3 (Br 2 -phen)], respectively. We have further evaluated photophysical properties of [Eu(acac) 3 (Br 2 -phen)] theoretically from the optimized sparkle structure and steady-state emission spectrum of Eu(III) complex. The intramolecular energy transfer (W ET ) and back-energy transfer (W BT ) rate predicted from the calculated singlet (S 1 ) and triplet (T 1 ) levels to the emissive 5 D 1 and 5 D 0 states for Eu(III) follow the path S 0 → S 1 → T 1 → 5 D 1 → 5 D 0 → 7 F 0,4 . The Eu(III) complex showed large stimulated emission cross-section (σ (0→2) = 1.27 × 10 −20 cm 2 ) similar to Nd-glass laser (1.6–4.5 × 10 −20 cm 2 ) and offers promise for high-power laser medium.
AB - Two new octa-coordinated red emitting complexes of the type [Ln(acac) 3 (Br 2 -phen)] [acac: acetylacetonate, Br 2 -phen: 4,7-dibromo-1,10-phenanthroline, Ln: Sm(III) and Eu(III)] have been synthesized and characterized. Single crystal X-ray diffraction (SCXD) of [Eu(acac) 3 (Br 2 -phen)] and [Eu(acac) 3 (H 2 O) 2 ](H 2 O) revealed distorted square antiprism structure for both complexes. 2D fingerprint plots and Hirshfeld surface analyses signify important interactions in crystal packing [H⋯H (72.2%), O⋯H/H⋯O (18.9%) and C⋯H/H⋯C (6.7%) contacts for [Eu(acac) 3 (H 2 O) 2 ](H 2 O), while [Eu(acac) 3 (Br 2 -phen)] showed H⋯H (40.5%), Br⋯H/H⋯Br (12.9%) and O⋯H/H⋯O (6.5%)] contacts]. Photophysical measurements gave quantum yield (Q Ln L ) of 1.1 and 13% with corresponding luminescence lifetime (τ obs ) of 38.76 ± 0.61 μs and 790 ± 1.53 μs for [Sm(acac) 3 (Br 2 -phen)] and [Eu(acac) 3 (Br 2 -phen)], respectively. We have further evaluated photophysical properties of [Eu(acac) 3 (Br 2 -phen)] theoretically from the optimized sparkle structure and steady-state emission spectrum of Eu(III) complex. The intramolecular energy transfer (W ET ) and back-energy transfer (W BT ) rate predicted from the calculated singlet (S 1 ) and triplet (T 1 ) levels to the emissive 5 D 1 and 5 D 0 states for Eu(III) follow the path S 0 → S 1 → T 1 → 5 D 1 → 5 D 0 → 7 F 0,4 . The Eu(III) complex showed large stimulated emission cross-section (σ (0→2) = 1.27 × 10 −20 cm 2 ) similar to Nd-glass laser (1.6–4.5 × 10 −20 cm 2 ) and offers promise for high-power laser medium.
KW - Hirshfeld surface analysis
KW - Lanthanide
KW - Laser properties
KW - β-Diketone
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U2 - 10.1016/j.jphotochem.2019.03.036
DO - 10.1016/j.jphotochem.2019.03.036
M3 - Article
AN - SCOPUS:85064173902
SN - 1010-6030
VL - 377
SP - 268
EP - 281
JO - Journal of Photochemistry and Photobiology A: Chemistry
JF - Journal of Photochemistry and Photobiology A: Chemistry
ER -