XAFS study of gadolinium and samarium bisporphyrinate complexes

J. H. Agondanou; G. A. Spyroulias; J. Purans; G. Tsikalas; C. Souleau; A. G. Coutsolelos; S. Bénazeth

doi:10.1021/ic000410o

XAFS study of gadolinium and samarium bisporphyrinate complexes

J. H. Agondanou
, G. A. Spyroulias
, J. Purans
, G. Tsikalas
, C. Souleau
, A. G. Coutsolelos^*
, S. Bénazeth

^*Corresponding author for this work

Thin Films Laboratory, Institute of Solid State Physics

Université Paris-Saclay
University of Crete
Université Paris Cité

Research output: Contribution to journal › Article › peer-review

18 Citations (Scopus)

Abstract

The comparative X-ray absorption spectroscopy study of gadolinium and samarium bisporphyrinate complexes represented by the formulas Gd^IIIH(oep)(tpp),Gd^III(oep)₂, Gd^IIIH(tpp)₂ and Sm^IIIH(oep)(tpp), Sm^III(oep)₂, Sm^IIIH(tpp)₂ is reported. The XAFS spectra are recorded on the LURE-DCI storage ring (Orsay, France) in transmission mode on the microcrystalline samples at the Gd and Sm L₃ edges. The local environment for Ln³⁺ ions has been reconstructed applying one-shell and two-shell XAFS analysis procedures. The protonated and nonprotonated bisporphyrinate complexes present different XAFS features. After our analysis on the title derivatives, the gadolinium ion (at 80 K) is found to be bonded: (i) to eight nitrogen atoms at R(Gd-N) 2.50 Å, for Gd^III(oep)₂ [Debye-Waller (DW) factor 0.004 Å; (ii) to seven nitrogen atoms at R(Gd-N) 2.49 Å, for Gd^IIIH(oep)(tpp) [DW factor 0.005 Å²] and one nitrogen at long distance; and (iii) to six nitrogen atoms at R(Gd-N) 2.50 Å [DW factor 0.006 Å²] and two nitrogen atoms at long distance for Gd^IIIH(tpp)₂. A similar coordination sphere has been detected for the corresponding Sm derivatives. So, the samarium ion (at room temperature) is bonded: (i) to eight nitrogen atoms at R(Sm-N) 2.53 Å, for Sm^III(oep)₂ [DW factor 0.006 Å²]; (ii) to seven nitrogen atoms at R(Sm-N) 2.53 Å, for Sm^IIIH(oep)(tpp) [DW factor 0.006 Å²] and one nitrogen at long distance; and (iii) to six nitrogen atoms at R(Sm-N) 2.50 Å, for Sm^IIIH(tpp)₂ [DW factor 0.006 Å²] and two nitrogen atoms at long distance. As far as concerns Ln^III(oep)₂ complexes, the increase of Ln-N distance in the series Gd³⁺ < Eu³⁺ < Sm³⁺ reflects an increase in the ionic radii, which are in good agreement with previously published XRD data on Eu^III(oep)₂. Moreover, the protonated Ln^IIIH(oep)(tpp) and Ln^IIIH(tpp)₂ complexes possess systematically shorter distances of about 0.02 Å between the XAFS and XRD data. This difference is attributed to the asymmetry of the distribution concerning Ln-N distances.

Original language	English
Pages (from-to)	6088-6096
Number of pages	9
Journal	Inorganic Chemistry
Volume	40
Issue number	24
DOIs	https://doi.org/10.1021/ic000410o
Publication status	Published - 19 Nov 2001

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10.1021/ic000410o

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@article{bcec858f13f84bd5845b161e8ab465b0,

title = "XAFS study of gadolinium and samarium bisporphyrinate complexes",

abstract = "The comparative X-ray absorption spectroscopy study of gadolinium and samarium bisporphyrinate complexes represented by the formulas GdIIIH(oep)(tpp),GdIII(oep)2, GdIIIH(tpp)2 and SmIIIH(oep)(tpp), SmIII(oep)2, SmIIIH(tpp)2 is reported. The XAFS spectra are recorded on the LURE-DCI storage ring (Orsay, France) in transmission mode on the microcrystalline samples at the Gd and Sm L3 edges. The local environment for Ln3+ ions has been reconstructed applying one-shell and two-shell XAFS analysis procedures. The protonated and nonprotonated bisporphyrinate complexes present different XAFS features. After our analysis on the title derivatives, the gadolinium ion (at 80 K) is found to be bonded: (i) to eight nitrogen atoms at R(Gd-N) 2.50 {\AA}, for GdIII(oep)2 [Debye-Waller (DW) factor 0.004 {\AA}; (ii) to seven nitrogen atoms at R(Gd-N) 2.49 {\AA}, for GdIIIH(oep)(tpp) [DW factor 0.005 {\AA}2] and one nitrogen at long distance; and (iii) to six nitrogen atoms at R(Gd-N) 2.50 {\AA} [DW factor 0.006 {\AA}2] and two nitrogen atoms at long distance for GdIIIH(tpp)2. A similar coordination sphere has been detected for the corresponding Sm derivatives. So, the samarium ion (at room temperature) is bonded: (i) to eight nitrogen atoms at R(Sm-N) 2.53 {\AA}, for SmIII(oep)2 [DW factor 0.006 {\AA}2]; (ii) to seven nitrogen atoms at R(Sm-N) 2.53 {\AA}, for SmIIIH(oep)(tpp) [DW factor 0.006 {\AA}2] and one nitrogen at long distance; and (iii) to six nitrogen atoms at R(Sm-N) 2.50 {\AA}, for SmIIIH(tpp)2 [DW factor 0.006 {\AA}2] and two nitrogen atoms at long distance. As far as concerns LnIII(oep)2 complexes, the increase of Ln-N distance in the series Gd3+ < Eu3+ < Sm3+ reflects an increase in the ionic radii, which are in good agreement with previously published XRD data on EuIII(oep)2. Moreover, the protonated LnIIIH(oep)(tpp) and LnIIIH(tpp)2 complexes possess systematically shorter distances of about 0.02 {\AA} between the XAFS and XRD data. This difference is attributed to the asymmetry of the distribution concerning Ln-N distances.",

author = "Agondanou, \{J. H.\} and Spyroulias, \{G. A.\} and J. Purans and G. Tsikalas and C. Souleau and Coutsolelos, \{A. G.\} and S. B{\'e}nazeth",

year = "2001",

month = nov,

day = "19",

doi = "10.1021/ic000410o",

language = "English",

volume = "40",

pages = "6088--6096",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "24",

}

TY - JOUR

T1 - XAFS study of gadolinium and samarium bisporphyrinate complexes

AU - Agondanou, J. H.

AU - Spyroulias, G. A.

AU - Purans, J.

AU - Tsikalas, G.

AU - Souleau, C.

AU - Coutsolelos, A. G.

AU - Bénazeth, S.

PY - 2001/11/19

Y1 - 2001/11/19

N2 - The comparative X-ray absorption spectroscopy study of gadolinium and samarium bisporphyrinate complexes represented by the formulas GdIIIH(oep)(tpp),GdIII(oep)2, GdIIIH(tpp)2 and SmIIIH(oep)(tpp), SmIII(oep)2, SmIIIH(tpp)2 is reported. The XAFS spectra are recorded on the LURE-DCI storage ring (Orsay, France) in transmission mode on the microcrystalline samples at the Gd and Sm L3 edges. The local environment for Ln3+ ions has been reconstructed applying one-shell and two-shell XAFS analysis procedures. The protonated and nonprotonated bisporphyrinate complexes present different XAFS features. After our analysis on the title derivatives, the gadolinium ion (at 80 K) is found to be bonded: (i) to eight nitrogen atoms at R(Gd-N) 2.50 Å, for GdIII(oep)2 [Debye-Waller (DW) factor 0.004 Å; (ii) to seven nitrogen atoms at R(Gd-N) 2.49 Å, for GdIIIH(oep)(tpp) [DW factor 0.005 Å2] and one nitrogen at long distance; and (iii) to six nitrogen atoms at R(Gd-N) 2.50 Å [DW factor 0.006 Å2] and two nitrogen atoms at long distance for GdIIIH(tpp)2. A similar coordination sphere has been detected for the corresponding Sm derivatives. So, the samarium ion (at room temperature) is bonded: (i) to eight nitrogen atoms at R(Sm-N) 2.53 Å, for SmIII(oep)2 [DW factor 0.006 Å2]; (ii) to seven nitrogen atoms at R(Sm-N) 2.53 Å, for SmIIIH(oep)(tpp) [DW factor 0.006 Å2] and one nitrogen at long distance; and (iii) to six nitrogen atoms at R(Sm-N) 2.50 Å, for SmIIIH(tpp)2 [DW factor 0.006 Å2] and two nitrogen atoms at long distance. As far as concerns LnIII(oep)2 complexes, the increase of Ln-N distance in the series Gd3+ < Eu3+ < Sm3+ reflects an increase in the ionic radii, which are in good agreement with previously published XRD data on EuIII(oep)2. Moreover, the protonated LnIIIH(oep)(tpp) and LnIIIH(tpp)2 complexes possess systematically shorter distances of about 0.02 Å between the XAFS and XRD data. This difference is attributed to the asymmetry of the distribution concerning Ln-N distances.

AB - The comparative X-ray absorption spectroscopy study of gadolinium and samarium bisporphyrinate complexes represented by the formulas GdIIIH(oep)(tpp),GdIII(oep)2, GdIIIH(tpp)2 and SmIIIH(oep)(tpp), SmIII(oep)2, SmIIIH(tpp)2 is reported. The XAFS spectra are recorded on the LURE-DCI storage ring (Orsay, France) in transmission mode on the microcrystalline samples at the Gd and Sm L3 edges. The local environment for Ln3+ ions has been reconstructed applying one-shell and two-shell XAFS analysis procedures. The protonated and nonprotonated bisporphyrinate complexes present different XAFS features. After our analysis on the title derivatives, the gadolinium ion (at 80 K) is found to be bonded: (i) to eight nitrogen atoms at R(Gd-N) 2.50 Å, for GdIII(oep)2 [Debye-Waller (DW) factor 0.004 Å; (ii) to seven nitrogen atoms at R(Gd-N) 2.49 Å, for GdIIIH(oep)(tpp) [DW factor 0.005 Å2] and one nitrogen at long distance; and (iii) to six nitrogen atoms at R(Gd-N) 2.50 Å [DW factor 0.006 Å2] and two nitrogen atoms at long distance for GdIIIH(tpp)2. A similar coordination sphere has been detected for the corresponding Sm derivatives. So, the samarium ion (at room temperature) is bonded: (i) to eight nitrogen atoms at R(Sm-N) 2.53 Å, for SmIII(oep)2 [DW factor 0.006 Å2]; (ii) to seven nitrogen atoms at R(Sm-N) 2.53 Å, for SmIIIH(oep)(tpp) [DW factor 0.006 Å2] and one nitrogen at long distance; and (iii) to six nitrogen atoms at R(Sm-N) 2.50 Å, for SmIIIH(tpp)2 [DW factor 0.006 Å2] and two nitrogen atoms at long distance. As far as concerns LnIII(oep)2 complexes, the increase of Ln-N distance in the series Gd3+ < Eu3+ < Sm3+ reflects an increase in the ionic radii, which are in good agreement with previously published XRD data on EuIII(oep)2. Moreover, the protonated LnIIIH(oep)(tpp) and LnIIIH(tpp)2 complexes possess systematically shorter distances of about 0.02 Å between the XAFS and XRD data. This difference is attributed to the asymmetry of the distribution concerning Ln-N distances.

UR - https://www.scopus.com/pages/publications/0035914685

U2 - 10.1021/ic000410o

DO - 10.1021/ic000410o

M3 - Article

AN - SCOPUS:0035914685

SN - 0020-1669

VL - 40

SP - 6088

EP - 6096

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 24

ER -

XAFS study of gadolinium and samarium bisporphyrinate complexes

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