Spectroscopic investigations of Eu3+ -complexes with ligands containing multipe diglycolamide pendant arms in a room temperature ionic liquid

A Sengupta, P.K. Mohapatra, M. Iqbal, Jurriaan Huskens, Willem Verboom

Research output: Contribution to journalArticleAcademicpeer-review

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Abstract

Fluorescence spectroscopy was used to study the complexation of different ligands containing multiple diglycolamide (DGA) pendent arms such as T-DGA (tripodal diglycolamide), C4DGA (upper rim functionalized calix [4] arene with four DGA moieties), and C8DGA (both side functionalized calix [4] arene with eight DGA moieties) with Eu3+ in ionic liquids such as C4mimNTf2 and C8mimNTf2 (1-alkyl-3-methylimidazolium bis(trifluoromethylsulphonyl)imide). Mainly five sets of emission profiles were observed in all the spectra (1st set at~580 nm assigned as the 5D0→7F0 transition, 2nd set at~593 nm assigned as the 5D0→7F1 transition, 3rd set at~613 nm assigned as the 5D0→7F2 transition, 4th set at~650 nm assigned as the 5D0→7F3 transition, and 5th set at~700 nm assigned as the 5D0→7F4 transition). The difference in the spectral features revealed that the nature of the complexes differs significantly from one another. Judd–Offelt constant Ω2, which is a measure of the covalency of the metal–ligand bond, follows the order Eu3+–C4DGA (C8mimNTf2)>Eu3+–C8DGA (C8mimNTf2)>Eu3+–TODGA (C4mimNTf2)>Eu3+–T-DGA (C4mimNTf2)>Eu3+aq. The high intensity of the 5D0→7F2 transitions in all complexes suggests that Eu3+ resides in a highly asymmetric environment. From the splitting patterns of the transitions, the local site symmetry around Eu3+ was found to be C2V for the Eu3+–T-DGA complex in both C4mimNTf2 and a 1:5 acetonitrile–water mixture, C4V for Eu3+–C8DGA and Eu3+–TODGA complexes, and either C1, C2, or CS for the Eu3+–C4DGA complex. A linear relationship between the 5D0–7F1 splitting vs E(5D0–7F0) and E(5D0–7F0) vs E(5D0–7F1) was observed. The crystal field parameters in the different complexes follow the trend Eu3+–C4DGA>Eu3+–TODGA>Eu3+–T-DGA in C4mimNTf2~Eu3+–C8DGA>Eu3+–T-DGA in 5:1 acetonitrile-water mixture.
Original languageUndefined
Pages (from-to)392-401
Number of pages10
JournalJournal of luminescence
Volume154
DOIs
Publication statusPublished - 2014

Keywords

  • METIS-308490
  • IR-95096

Cite this

@article{e7340d988e2a490386cae2cdb8ef4693,
title = "Spectroscopic investigations of Eu3+ -complexes with ligands containing multipe diglycolamide pendant arms in a room temperature ionic liquid",
abstract = "Fluorescence spectroscopy was used to study the complexation of different ligands containing multiple diglycolamide (DGA) pendent arms such as T-DGA (tripodal diglycolamide), C4DGA (upper rim functionalized calix [4] arene with four DGA moieties), and C8DGA (both side functionalized calix [4] arene with eight DGA moieties) with Eu3+ in ionic liquids such as C4mimNTf2 and C8mimNTf2 (1-alkyl-3-methylimidazolium bis(trifluoromethylsulphonyl)imide). Mainly five sets of emission profiles were observed in all the spectra (1st set at~580 nm assigned as the 5D0→7F0 transition, 2nd set at~593 nm assigned as the 5D0→7F1 transition, 3rd set at~613 nm assigned as the 5D0→7F2 transition, 4th set at~650 nm assigned as the 5D0→7F3 transition, and 5th set at~700 nm assigned as the 5D0→7F4 transition). The difference in the spectral features revealed that the nature of the complexes differs significantly from one another. Judd–Offelt constant Ω2, which is a measure of the covalency of the metal–ligand bond, follows the order Eu3+–C4DGA (C8mimNTf2)>Eu3+–C8DGA (C8mimNTf2)>Eu3+–TODGA (C4mimNTf2)>Eu3+–T-DGA (C4mimNTf2)>Eu3+aq. The high intensity of the 5D0→7F2 transitions in all complexes suggests that Eu3+ resides in a highly asymmetric environment. From the splitting patterns of the transitions, the local site symmetry around Eu3+ was found to be C2V for the Eu3+–T-DGA complex in both C4mimNTf2 and a 1:5 acetonitrile–water mixture, C4V for Eu3+–C8DGA and Eu3+–TODGA complexes, and either C1, C2, or CS for the Eu3+–C4DGA complex. A linear relationship between the 5D0–7F1 splitting vs E(5D0–7F0) and E(5D0–7F0) vs E(5D0–7F1) was observed. The crystal field parameters in the different complexes follow the trend Eu3+–C4DGA>Eu3+–TODGA>Eu3+–T-DGA in C4mimNTf2~Eu3+–C8DGA>Eu3+–T-DGA in 5:1 acetonitrile-water mixture.",
keywords = "METIS-308490, IR-95096",
author = "A Sengupta and P.K. Mohapatra and M. Iqbal and Jurriaan Huskens and Willem Verboom",
year = "2014",
doi = "10.1016/j.jlumin.2014.05.001",
language = "Undefined",
volume = "154",
pages = "392--401",
journal = "Journal of luminescence",
issn = "0022-2313",
publisher = "Elsevier",

}

Spectroscopic investigations of Eu3+ -complexes with ligands containing multipe diglycolamide pendant arms in a room temperature ionic liquid. / Sengupta, A; Mohapatra, P.K.; Iqbal, M.; Huskens, Jurriaan; Verboom, Willem.

In: Journal of luminescence, Vol. 154, 2014, p. 392-401.

Research output: Contribution to journalArticleAcademicpeer-review

TY - JOUR

T1 - Spectroscopic investigations of Eu3+ -complexes with ligands containing multipe diglycolamide pendant arms in a room temperature ionic liquid

AU - Sengupta, A

AU - Mohapatra, P.K.

AU - Iqbal, M.

AU - Huskens, Jurriaan

AU - Verboom, Willem

PY - 2014

Y1 - 2014

N2 - Fluorescence spectroscopy was used to study the complexation of different ligands containing multiple diglycolamide (DGA) pendent arms such as T-DGA (tripodal diglycolamide), C4DGA (upper rim functionalized calix [4] arene with four DGA moieties), and C8DGA (both side functionalized calix [4] arene with eight DGA moieties) with Eu3+ in ionic liquids such as C4mimNTf2 and C8mimNTf2 (1-alkyl-3-methylimidazolium bis(trifluoromethylsulphonyl)imide). Mainly five sets of emission profiles were observed in all the spectra (1st set at~580 nm assigned as the 5D0→7F0 transition, 2nd set at~593 nm assigned as the 5D0→7F1 transition, 3rd set at~613 nm assigned as the 5D0→7F2 transition, 4th set at~650 nm assigned as the 5D0→7F3 transition, and 5th set at~700 nm assigned as the 5D0→7F4 transition). The difference in the spectral features revealed that the nature of the complexes differs significantly from one another. Judd–Offelt constant Ω2, which is a measure of the covalency of the metal–ligand bond, follows the order Eu3+–C4DGA (C8mimNTf2)>Eu3+–C8DGA (C8mimNTf2)>Eu3+–TODGA (C4mimNTf2)>Eu3+–T-DGA (C4mimNTf2)>Eu3+aq. The high intensity of the 5D0→7F2 transitions in all complexes suggests that Eu3+ resides in a highly asymmetric environment. From the splitting patterns of the transitions, the local site symmetry around Eu3+ was found to be C2V for the Eu3+–T-DGA complex in both C4mimNTf2 and a 1:5 acetonitrile–water mixture, C4V for Eu3+–C8DGA and Eu3+–TODGA complexes, and either C1, C2, or CS for the Eu3+–C4DGA complex. A linear relationship between the 5D0–7F1 splitting vs E(5D0–7F0) and E(5D0–7F0) vs E(5D0–7F1) was observed. The crystal field parameters in the different complexes follow the trend Eu3+–C4DGA>Eu3+–TODGA>Eu3+–T-DGA in C4mimNTf2~Eu3+–C8DGA>Eu3+–T-DGA in 5:1 acetonitrile-water mixture.

AB - Fluorescence spectroscopy was used to study the complexation of different ligands containing multiple diglycolamide (DGA) pendent arms such as T-DGA (tripodal diglycolamide), C4DGA (upper rim functionalized calix [4] arene with four DGA moieties), and C8DGA (both side functionalized calix [4] arene with eight DGA moieties) with Eu3+ in ionic liquids such as C4mimNTf2 and C8mimNTf2 (1-alkyl-3-methylimidazolium bis(trifluoromethylsulphonyl)imide). Mainly five sets of emission profiles were observed in all the spectra (1st set at~580 nm assigned as the 5D0→7F0 transition, 2nd set at~593 nm assigned as the 5D0→7F1 transition, 3rd set at~613 nm assigned as the 5D0→7F2 transition, 4th set at~650 nm assigned as the 5D0→7F3 transition, and 5th set at~700 nm assigned as the 5D0→7F4 transition). The difference in the spectral features revealed that the nature of the complexes differs significantly from one another. Judd–Offelt constant Ω2, which is a measure of the covalency of the metal–ligand bond, follows the order Eu3+–C4DGA (C8mimNTf2)>Eu3+–C8DGA (C8mimNTf2)>Eu3+–TODGA (C4mimNTf2)>Eu3+–T-DGA (C4mimNTf2)>Eu3+aq. The high intensity of the 5D0→7F2 transitions in all complexes suggests that Eu3+ resides in a highly asymmetric environment. From the splitting patterns of the transitions, the local site symmetry around Eu3+ was found to be C2V for the Eu3+–T-DGA complex in both C4mimNTf2 and a 1:5 acetonitrile–water mixture, C4V for Eu3+–C8DGA and Eu3+–TODGA complexes, and either C1, C2, or CS for the Eu3+–C4DGA complex. A linear relationship between the 5D0–7F1 splitting vs E(5D0–7F0) and E(5D0–7F0) vs E(5D0–7F1) was observed. The crystal field parameters in the different complexes follow the trend Eu3+–C4DGA>Eu3+–TODGA>Eu3+–T-DGA in C4mimNTf2~Eu3+–C8DGA>Eu3+–T-DGA in 5:1 acetonitrile-water mixture.

KW - METIS-308490

KW - IR-95096

U2 - 10.1016/j.jlumin.2014.05.001

DO - 10.1016/j.jlumin.2014.05.001

M3 - Article

VL - 154

SP - 392

EP - 401

JO - Journal of luminescence

JF - Journal of luminescence

SN - 0022-2313

ER -