Continuous-wave single-crystal electron paramagnetic resonance of adsorption of gases to cupric ions in the Zn(II)-Doped Porous Coordination Polymer Cu2.965Zn0.035(btc)2

Stefan Friedländer; Petko St Petkov; Felix Bolling; Anastasia Kultaeva; Winfried Böhlmann; Oleg Ovchar; Anatolii G. Belous; Thomas Heine; Andreas Poppl

doi:10.1021/acs.jpcc.6b09456

Continuous-wave single-crystal electron paramagnetic resonance of adsorption of gases to cupric ions in the Zn(II)-Doped Porous Coordination Polymer Cu_2.965Zn_0.035(btc)₂

Stefan Friedländer, Petko St Petkov, Felix Bolling, Anastasia Kultaeva, Winfried Böhlmann, Oleg Ovchar, Anatolii G. Belous, Thomas Heine, Andreas Poppl

Department of Chemistry

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

10 Citations (Scopus)

Abstract

Continuous-wave X-band electron paramagnetic resonance with dielectric resonators has successfully been applied to small single crystals of the metal-organic framework HKUST-1 and Cu_2.965Zn_0.035(btc)₂ to investigate the structure of paddle-wheel building blocks with pure Cu/Cu and mixed Cu/Zn pairs. The local paramagnetic Cu²⁺ ion probes were used to identify the magnetic g and A tensor orientations with respect to the crystal axes. We were able to monitor changes in these tensor orientations by EPR at gas adsorption on MOFs for the first time. We explored the spectral simulations of the spin Hamilton parameters of the single crystals and found results similar to those in previous studies of powder samples, but moreover, the tensor orientations are influenced upon gas adsorption, which is represented by a distinct line broadening effect in the angular resolved single-crystal EPR spectra. The as-synthesized, dehydrated, carbon dioxide-adsorbed, carbon monoxide-adsorbed, methanol-adsorbed, and reactivated states have been analyzed to reveal the magnetic tensor orientations, and the direct coordination of the adsorbed gas to the Cu²⁺ ions along with consistent, corresponding DFT calculations allows us to predict an improved model for the mixed paddle-wheel structure upon the adsorption of gases to a paddle-wheel based on perturbations of the g and A principal axis orientations. Additionally, we analyzed a reversibly occurring background signal observable not only in Cu_2.965Zn_0.035(btc)₂ but also in pure Cu₃(btc)₂ at very low temperatures.

Original language	English
Pages (from-to)	27399-27411
Number of pages	13
Journal	Journal of Physical Chemistry C
Volume	120
Issue number	48
DOIs	https://doi.org/10.1021/acs.jpcc.6b09456
Publication status	Published - 2016 Dec 8

Bibliographical note

Funding Information:
The authors gratefully acknowledge financial support within the priority programs SPP 1362 (Porose metallorganische Gerustverbindungen) and 1601 (Increasing Sensitivity with EPR) of the Deutsche Forschungsgemeinschaft (DFG) and support by the Center for Information Services and High Performance Computing (ZIH) at Technische Universitat Dresden for the provided computational resources. The authors thank the group of Stefan Kaskel, Technische Universitat Dresden, for providing and characterizing the samples.

Funding Information:
The authors gratefully acknowledge financial support within the priority programs SPP 1362 (Poröse metallorganische Ger-üstverbindungen) and 1601 (Increasing Sensitivity with EPR) of the Deutsche Forschungsgemeinschaft (DFG) and support by the Center for Information Services and High Performance Computing (ZIH) at Technische Universitaẗ Dresden for the provided computational resources. The authors thank the group of Stefan Kaskel, Technische Universitaẗ Dresden, for providing and characterizing the samples.

Publisher Copyright:
© 2016 American Chemical Society.

All Science Journal Classification (ASJC) codes

Electronic, Optical and Magnetic Materials
Energy(all)
Physical and Theoretical Chemistry
Surfaces, Coatings and Films

Access to Document

10.1021/acs.jpcc.6b09456

Cite this

Friedländer, S., Petkov, P. S., Bolling, F., Kultaeva, A., Böhlmann, W., Ovchar, O., Belous, A. G., Heine, T., & Poppl, A. (2016). Continuous-wave single-crystal electron paramagnetic resonance of adsorption of gases to cupric ions in the Zn(II)-Doped Porous Coordination Polymer Cu_2.965Zn_0.035(btc)₂. Journal of Physical Chemistry C, 120(48), 27399-27411. https://doi.org/10.1021/acs.jpcc.6b09456

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title = "Continuous-wave single-crystal electron paramagnetic resonance of adsorption of gases to cupric ions in the Zn(II)-Doped Porous Coordination Polymer Cu2.965Zn0.035(btc)2",

abstract = "Continuous-wave X-band electron paramagnetic resonance with dielectric resonators has successfully been applied to small single crystals of the metal-organic framework HKUST-1 and Cu2.965Zn0.035(btc)2 to investigate the structure of paddle-wheel building blocks with pure Cu/Cu and mixed Cu/Zn pairs. The local paramagnetic Cu2+ ion probes were used to identify the magnetic g and A tensor orientations with respect to the crystal axes. We were able to monitor changes in these tensor orientations by EPR at gas adsorption on MOFs for the first time. We explored the spectral simulations of the spin Hamilton parameters of the single crystals and found results similar to those in previous studies of powder samples, but moreover, the tensor orientations are influenced upon gas adsorption, which is represented by a distinct line broadening effect in the angular resolved single-crystal EPR spectra. The as-synthesized, dehydrated, carbon dioxide-adsorbed, carbon monoxide-adsorbed, methanol-adsorbed, and reactivated states have been analyzed to reveal the magnetic tensor orientations, and the direct coordination of the adsorbed gas to the Cu2+ ions along with consistent, corresponding DFT calculations allows us to predict an improved model for the mixed paddle-wheel structure upon the adsorption of gases to a paddle-wheel based on perturbations of the g and A principal axis orientations. Additionally, we analyzed a reversibly occurring background signal observable not only in Cu2.965Zn0.035(btc)2 but also in pure Cu3(btc)2 at very low temperatures.",

author = "Stefan Friedl{\"a}nder and Petkov, {Petko St} and Felix Bolling and Anastasia Kultaeva and Winfried B{\"o}hlmann and Oleg Ovchar and Belous, {Anatolii G.} and Thomas Heine and Andreas Poppl",

note = "Funding Information: The authors gratefully acknowledge financial support within the priority programs SPP 1362 (Porose metallorganische Gerustverbindungen) and 1601 (Increasing Sensitivity with EPR) of the Deutsche Forschungsgemeinschaft (DFG) and support by the Center for Information Services and High Performance Computing (ZIH) at Technische Universitat Dresden for the provided computational resources. The authors thank the group of Stefan Kaskel, Technische Universitat Dresden, for providing and characterizing the samples. Funding Information: The authors gratefully acknowledge financial support within the priority programs SPP 1362 (Por{\"o}se metallorganische Ger-{\"u}stverbindungen) and 1601 (Increasing Sensitivity with EPR) of the Deutsche Forschungsgemeinschaft (DFG) and support by the Center for Information Services and High Performance Computing (ZIH) at Technische Universitaẗ Dresden for the provided computational resources. The authors thank the group of Stefan Kaskel, Technische Universitaẗ Dresden, for providing and characterizing the samples. Publisher Copyright: {\textcopyright} 2016 American Chemical Society.",

year = "2016",

month = dec,

day = "8",

doi = "10.1021/acs.jpcc.6b09456",

language = "English",

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Friedländer, S, Petkov, PS, Bolling, F, Kultaeva, A, Böhlmann, W, Ovchar, O, Belous, AG, Heine, T & Poppl, A 2016, 'Continuous-wave single-crystal electron paramagnetic resonance of adsorption of gases to cupric ions in the Zn(II)-Doped Porous Coordination Polymer Cu_2.965Zn_0.035(btc)₂', Journal of Physical Chemistry C, vol. 120, no. 48, pp. 27399-27411. https://doi.org/10.1021/acs.jpcc.6b09456

Continuous-wave single-crystal electron paramagnetic resonance of adsorption of gases to cupric ions in the Zn(II)-Doped Porous Coordination Polymer Cu_2.965Zn_0.035(btc)₂. / Friedländer, Stefan; Petkov, Petko St; Bolling, Felix et al.

In: Journal of Physical Chemistry C, Vol. 120, No. 48, 08.12.2016, p. 27399-27411.

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

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T1 - Continuous-wave single-crystal electron paramagnetic resonance of adsorption of gases to cupric ions in the Zn(II)-Doped Porous Coordination Polymer Cu2.965Zn0.035(btc)2

AU - Friedländer, Stefan

AU - Petkov, Petko St

AU - Bolling, Felix

AU - Kultaeva, Anastasia

AU - Böhlmann, Winfried

AU - Ovchar, Oleg

AU - Belous, Anatolii G.

AU - Heine, Thomas

AU - Poppl, Andreas

N1 - Funding Information: The authors gratefully acknowledge financial support within the priority programs SPP 1362 (Porose metallorganische Gerustverbindungen) and 1601 (Increasing Sensitivity with EPR) of the Deutsche Forschungsgemeinschaft (DFG) and support by the Center for Information Services and High Performance Computing (ZIH) at Technische Universitat Dresden for the provided computational resources. The authors thank the group of Stefan Kaskel, Technische Universitat Dresden, for providing and characterizing the samples. Funding Information: The authors gratefully acknowledge financial support within the priority programs SPP 1362 (Poröse metallorganische Ger-üstverbindungen) and 1601 (Increasing Sensitivity with EPR) of the Deutsche Forschungsgemeinschaft (DFG) and support by the Center for Information Services and High Performance Computing (ZIH) at Technische Universitaẗ Dresden for the provided computational resources. The authors thank the group of Stefan Kaskel, Technische Universitaẗ Dresden, for providing and characterizing the samples. Publisher Copyright: © 2016 American Chemical Society.

PY - 2016/12/8

Y1 - 2016/12/8

N2 - Continuous-wave X-band electron paramagnetic resonance with dielectric resonators has successfully been applied to small single crystals of the metal-organic framework HKUST-1 and Cu2.965Zn0.035(btc)2 to investigate the structure of paddle-wheel building blocks with pure Cu/Cu and mixed Cu/Zn pairs. The local paramagnetic Cu2+ ion probes were used to identify the magnetic g and A tensor orientations with respect to the crystal axes. We were able to monitor changes in these tensor orientations by EPR at gas adsorption on MOFs for the first time. We explored the spectral simulations of the spin Hamilton parameters of the single crystals and found results similar to those in previous studies of powder samples, but moreover, the tensor orientations are influenced upon gas adsorption, which is represented by a distinct line broadening effect in the angular resolved single-crystal EPR spectra. The as-synthesized, dehydrated, carbon dioxide-adsorbed, carbon monoxide-adsorbed, methanol-adsorbed, and reactivated states have been analyzed to reveal the magnetic tensor orientations, and the direct coordination of the adsorbed gas to the Cu2+ ions along with consistent, corresponding DFT calculations allows us to predict an improved model for the mixed paddle-wheel structure upon the adsorption of gases to a paddle-wheel based on perturbations of the g and A principal axis orientations. Additionally, we analyzed a reversibly occurring background signal observable not only in Cu2.965Zn0.035(btc)2 but also in pure Cu3(btc)2 at very low temperatures.

AB - Continuous-wave X-band electron paramagnetic resonance with dielectric resonators has successfully been applied to small single crystals of the metal-organic framework HKUST-1 and Cu2.965Zn0.035(btc)2 to investigate the structure of paddle-wheel building blocks with pure Cu/Cu and mixed Cu/Zn pairs. The local paramagnetic Cu2+ ion probes were used to identify the magnetic g and A tensor orientations with respect to the crystal axes. We were able to monitor changes in these tensor orientations by EPR at gas adsorption on MOFs for the first time. We explored the spectral simulations of the spin Hamilton parameters of the single crystals and found results similar to those in previous studies of powder samples, but moreover, the tensor orientations are influenced upon gas adsorption, which is represented by a distinct line broadening effect in the angular resolved single-crystal EPR spectra. The as-synthesized, dehydrated, carbon dioxide-adsorbed, carbon monoxide-adsorbed, methanol-adsorbed, and reactivated states have been analyzed to reveal the magnetic tensor orientations, and the direct coordination of the adsorbed gas to the Cu2+ ions along with consistent, corresponding DFT calculations allows us to predict an improved model for the mixed paddle-wheel structure upon the adsorption of gases to a paddle-wheel based on perturbations of the g and A principal axis orientations. Additionally, we analyzed a reversibly occurring background signal observable not only in Cu2.965Zn0.035(btc)2 but also in pure Cu3(btc)2 at very low temperatures.

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