Sensing the Spin State of Room-Temperature Switchable Cyanometallate Frameworks with Nitrogen-Vacancy Centers in Nanodiamonds

Bradley
T. Flinn; Graham A. Rance; William J. Cull; Ian Cardillo-Zallo; Jem Pitcairn; Matthew J. Cliffe; Michael W. Fay; Ashley J. Tyler; Benjamin L. Weare; Craig T. Stoppiello; E. Stephen Davies; Melissa L. Mather; Andrei N. Khlobystov

doi:10.1021/acsnano.3c11820

Sensing the Spin State of Room-Temperature Switchable Cyanometallate Frameworks with Nitrogen-Vacancy Centers in Nanodiamonds

Bradley T. Flinn, Graham A. Rance, William J. Cull, Ian Cardillo-Zallo, Jem Pitcairn, Matthew J. Cliffe, Michael W. Fay, Ashley J. Tyler, Benjamin L. Weare, Craig T. Stoppiello, E. Stephen Davies, Melissa L. Mather^*, Andrei N. Khlobystov^*

^*Corresponding author for this work

Chemistry

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

Abstract

Room-temperature magnetically switchable materials play a vital role in current and upcoming quantum technologies, such as spintronics, molecular switches, and data storage devices. The increasing miniaturization of device architectures produces a need to develop analytical tools capable of precisely probing spin information at the single-particle level. In this work, we demonstrate a methodology using negatively charged nitrogen vacancies (NV–) in fluorescent nanodiamond (FND) particles to probe the magnetic switching of a spin crossover (SCO) metal–organic framework (MOF), [Fe(1,6-naphthyridine)2(Ag(CN)2)2] material (1), and a single-molecule photomagnet [X(18-crown-6)(H2O)3]Fe(CN)6·2H2O, where X = Eu and Dy (materials 2a and 2b, respectively), in response to heat, light, and electron beam exposure. We employ correlative light–electron microscopy using transmission electron microscopy (TEM) finder grids to accurately image and sense spin–spin interacting particles down to the single-particle level. We used surface-sensitive optically detected magnetic resonance (ODMR) and magnetic modulation (MM) of FND photoluminescence (PL) to sense spins to a distance of ca. 10–30 nm. We show that ODMR and MM sensing was not sensitive to the temperature-induced SCO of FeII in 1 as formation of paramagnetic FeIII through surface oxidation (detected by X-ray photoelectron spectroscopy) on heating obscured the signal of bulk SCO switching. We found that proximal FNDs could effectively sense the chemical transformations induced by the 200 keV electron beam in 1, namely, AgI → Ag0 and FeII → FeIII. However, transformations induced by the electron beam are irreversible as they substantially disrupt the structure of MOF particles. Finally, we demonstrate NV– sensing of reversible photomagnetic switching, FeIII + (18-crown-6) ⇆ FeII + (18-crown-6)+ •, triggered in 2a and 2b by 405 nm light. The photoredox process of 2a and 2b proved to be the best candidate for room-temperature single-particle magnetic switching utilizing FNDs as a sensor, which could have applications into next-generation quantum technologies.

Original language	English
Pages (from-to)	7148-7160
Number of pages	13
Journal	ACS Nano
Volume	18
Issue number	9
Early online date	21 Feb 2024
DOIs	https://doi.org/10.1021/acsnano.3c11820
Publication status	Published - 5 Mar 2024

Bibliographical note

Acknowledgments
B.T.F. acknowledges the support of the Engineering and Physical Science Research Council (EPSRC), and the Nanoscale and Microscale Research Centre (nmRC) for access to instrumentation JEOL 2100+ TEM, under Grant No. EP/L022494/1. OneView and K3-IS Gatan cameras were used under Grant No. EP/WOO6413/1. M.L.M. and A.J.T. wish to acknowledge the European Research Council (ERC) for funding through the ERC Consolidator Award, TransPhorm (Grant No. 683108). A.N.K. and M.L.M. wish to acknowledge funding from EPSRC through the New Horizons scheme (Grant No. EP/V049623/1), and A.N.K. acknowledges funding of the EPSRC Program Grant “Metal Atoms on Surfaces & Interfaces (MASI) for Sustainable Future” (Grant No. EP/V000055/1), and the Royal Society. C.T.S. acknowledges the facilities, and technical assistance of the Microscopy Australia Facility at the Centre for Microscopy and Microanalysis, The University of Queensland. M.L.M. wishes to acknowledge funding from the Royal Academy of Engineering through their Chair in Emerging Technologies Scheme (Grant No. CiET-2223-102). W.J.C., A.N.K., and M.L.M. acknowledge funding from the Leverhulme Trust (Grant No. RPG-2022-300: “Taming the Radicals: Highly Reactive Species Incarcerated in Carbon Cages”).

Keywords

spin-crossover
Nitrogen-vacancy sensing
metal−organic framework
nanodiamond
transmission electron microscopy
photomagnetism

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Flinn, B., Rance, G. A., Cull, W. J., Cardillo-Zallo, I., Pitcairn, J., Cliffe, M. J., Fay, M. W., Tyler, A. J., Weare, B. L., Stoppiello, C. T., Davies, E. S., Mather, M. L., & Khlobystov, A. N. (2024). Sensing the Spin State of Room-Temperature Switchable Cyanometallate Frameworks with Nitrogen-Vacancy Centers in Nanodiamonds. ACS Nano, 18(9), 7148-7160. https://doi.org/10.1021/acsnano.3c11820

@article{2779fcd2b2f145e7b685be8656aafce7,

title = "Sensing the Spin State of Room-Temperature Switchable Cyanometallate Frameworks with Nitrogen-Vacancy Centers in Nanodiamonds",

abstract = "Room-temperature magnetically switchable materials play a vital role in current and upcoming quantum technologies, such as spintronics, molecular switches, and data storage devices. The increasing miniaturization of device architectures produces a need to develop analytical tools capable of precisely probing spin information at the single-particle level. In this work, we demonstrate a methodology using negatively charged nitrogen vacancies (NV–) in fluorescent nanodiamond (FND) particles to probe the magnetic switching of a spin crossover (SCO) metal–organic framework (MOF), [Fe(1,6-naphthyridine)2(Ag(CN)2)2] material (1), and a single-molecule photomagnet [X(18-crown-6)(H2O)3]Fe(CN)6·2H2O, where X = Eu and Dy (materials 2a and 2b, respectively), in response to heat, light, and electron beam exposure. We employ correlative light–electron microscopy using transmission electron microscopy (TEM) finder grids to accurately image and sense spin–spin interacting particles down to the single-particle level. We used surface-sensitive optically detected magnetic resonance (ODMR) and magnetic modulation (MM) of FND photoluminescence (PL) to sense spins to a distance of ca. 10–30 nm. We show that ODMR and MM sensing was not sensitive to the temperature-induced SCO of FeII in 1 as formation of paramagnetic FeIII through surface oxidation (detected by X-ray photoelectron spectroscopy) on heating obscured the signal of bulk SCO switching. We found that proximal FNDs could effectively sense the chemical transformations induced by the 200 keV electron beam in 1, namely, AgI → Ag0 and FeII → FeIII. However, transformations induced by the electron beam are irreversible as they substantially disrupt the structure of MOF particles. Finally, we demonstrate NV– sensing of reversible photomagnetic switching, FeIII + (18-crown-6) ⇆ FeII + (18-crown-6)+ •, triggered in 2a and 2b by 405 nm light. The photoredox process of 2a and 2b proved to be the best candidate for room-temperature single-particle magnetic switching utilizing FNDs as a sensor, which could have applications into next-generation quantum technologies.",

keywords = "spin-crossover, Nitrogen-vacancy sensing, metal−organic framework, nanodiamond, transmission electron microscopy, photomagnetism",

author = "Flinn, {Bradley T.} and Rance, {Graham A.} and Cull, {William J.} and Ian Cardillo-Zallo and Jem Pitcairn and Cliffe, {Matthew J.} and Fay, {Michael W.} and Tyler, {Ashley J.} and Weare, {Benjamin L.} and Stoppiello, {Craig T.} and Davies, {E. Stephen} and Mather, {Melissa L.} and Khlobystov, {Andrei N.}",

note = "Acknowledgments B.T.F. acknowledges the support of the Engineering and Physical Science Research Council (EPSRC), and the Nanoscale and Microscale Research Centre (nmRC) for access to instrumentation JEOL 2100+ TEM, under Grant No. EP/L022494/1. OneView and K3-IS Gatan cameras were used under Grant No. EP/WOO6413/1. M.L.M. and A.J.T. wish to acknowledge the European Research Council (ERC) for funding through the ERC Consolidator Award, TransPhorm (Grant No. 683108). A.N.K. and M.L.M. wish to acknowledge funding from EPSRC through the New Horizons scheme (Grant No. EP/V049623/1), and A.N.K. acknowledges funding of the EPSRC Program Grant “Metal Atoms on Surfaces & Interfaces (MASI) for Sustainable Future” (Grant No. EP/V000055/1), and the Royal Society. C.T.S. acknowledges the facilities, and technical assistance of the Microscopy Australia Facility at the Centre for Microscopy and Microanalysis, The University of Queensland. M.L.M. wishes to acknowledge funding from the Royal Academy of Engineering through their Chair in Emerging Technologies Scheme (Grant No. CiET-2223-102). W.J.C., A.N.K., and M.L.M. acknowledge funding from the Leverhulme Trust (Grant No. RPG-2022-300: “Taming the Radicals: Highly Reactive Species Incarcerated in Carbon Cages”).",

year = "2024",

month = mar,

day = "5",

doi = "10.1021/acsnano.3c11820",

language = "English",

volume = "18",

pages = "7148--7160",

journal = "ACS Nano",

issn = "1936-0851",

publisher = "American Chemical Society",

number = "9",

}

Flinn, B, Rance, GA, Cull, WJ, Cardillo-Zallo, I, Pitcairn, J, Cliffe, MJ, Fay, MW, Tyler, AJ, Weare, BL, Stoppiello, CT, Davies, ES, Mather, ML & Khlobystov, AN 2024, 'Sensing the Spin State of Room-Temperature Switchable Cyanometallate Frameworks with Nitrogen-Vacancy Centers in Nanodiamonds', ACS Nano, vol. 18, no. 9, pp. 7148-7160. https://doi.org/10.1021/acsnano.3c11820

TY - JOUR

T1 - Sensing the Spin State of Room-Temperature Switchable Cyanometallate Frameworks with Nitrogen-Vacancy Centers in Nanodiamonds

AU - Flinn, Bradley T.

AU - Rance, Graham A.

AU - Cull, William J.

AU - Cardillo-Zallo, Ian

AU - Pitcairn, Jem

AU - Cliffe, Matthew J.

AU - Fay, Michael W.

AU - Tyler, Ashley J.

AU - Weare, Benjamin L.

AU - Stoppiello, Craig T.

AU - Davies, E. Stephen

AU - Mather, Melissa L.

AU - Khlobystov, Andrei N.

N1 - Acknowledgments B.T.F. acknowledges the support of the Engineering and Physical Science Research Council (EPSRC), and the Nanoscale and Microscale Research Centre (nmRC) for access to instrumentation JEOL 2100+ TEM, under Grant No. EP/L022494/1. OneView and K3-IS Gatan cameras were used under Grant No. EP/WOO6413/1. M.L.M. and A.J.T. wish to acknowledge the European Research Council (ERC) for funding through the ERC Consolidator Award, TransPhorm (Grant No. 683108). A.N.K. and M.L.M. wish to acknowledge funding from EPSRC through the New Horizons scheme (Grant No. EP/V049623/1), and A.N.K. acknowledges funding of the EPSRC Program Grant “Metal Atoms on Surfaces & Interfaces (MASI) for Sustainable Future” (Grant No. EP/V000055/1), and the Royal Society. C.T.S. acknowledges the facilities, and technical assistance of the Microscopy Australia Facility at the Centre for Microscopy and Microanalysis, The University of Queensland. M.L.M. wishes to acknowledge funding from the Royal Academy of Engineering through their Chair in Emerging Technologies Scheme (Grant No. CiET-2223-102). W.J.C., A.N.K., and M.L.M. acknowledge funding from the Leverhulme Trust (Grant No. RPG-2022-300: “Taming the Radicals: Highly Reactive Species Incarcerated in Carbon Cages”).

PY - 2024/3/5

Y1 - 2024/3/5

N2 - Room-temperature magnetically switchable materials play a vital role in current and upcoming quantum technologies, such as spintronics, molecular switches, and data storage devices. The increasing miniaturization of device architectures produces a need to develop analytical tools capable of precisely probing spin information at the single-particle level. In this work, we demonstrate a methodology using negatively charged nitrogen vacancies (NV–) in fluorescent nanodiamond (FND) particles to probe the magnetic switching of a spin crossover (SCO) metal–organic framework (MOF), [Fe(1,6-naphthyridine)2(Ag(CN)2)2] material (1), and a single-molecule photomagnet [X(18-crown-6)(H2O)3]Fe(CN)6·2H2O, where X = Eu and Dy (materials 2a and 2b, respectively), in response to heat, light, and electron beam exposure. We employ correlative light–electron microscopy using transmission electron microscopy (TEM) finder grids to accurately image and sense spin–spin interacting particles down to the single-particle level. We used surface-sensitive optically detected magnetic resonance (ODMR) and magnetic modulation (MM) of FND photoluminescence (PL) to sense spins to a distance of ca. 10–30 nm. We show that ODMR and MM sensing was not sensitive to the temperature-induced SCO of FeII in 1 as formation of paramagnetic FeIII through surface oxidation (detected by X-ray photoelectron spectroscopy) on heating obscured the signal of bulk SCO switching. We found that proximal FNDs could effectively sense the chemical transformations induced by the 200 keV electron beam in 1, namely, AgI → Ag0 and FeII → FeIII. However, transformations induced by the electron beam are irreversible as they substantially disrupt the structure of MOF particles. Finally, we demonstrate NV– sensing of reversible photomagnetic switching, FeIII + (18-crown-6) ⇆ FeII + (18-crown-6)+ •, triggered in 2a and 2b by 405 nm light. The photoredox process of 2a and 2b proved to be the best candidate for room-temperature single-particle magnetic switching utilizing FNDs as a sensor, which could have applications into next-generation quantum technologies.

AB - Room-temperature magnetically switchable materials play a vital role in current and upcoming quantum technologies, such as spintronics, molecular switches, and data storage devices. The increasing miniaturization of device architectures produces a need to develop analytical tools capable of precisely probing spin information at the single-particle level. In this work, we demonstrate a methodology using negatively charged nitrogen vacancies (NV–) in fluorescent nanodiamond (FND) particles to probe the magnetic switching of a spin crossover (SCO) metal–organic framework (MOF), [Fe(1,6-naphthyridine)2(Ag(CN)2)2] material (1), and a single-molecule photomagnet [X(18-crown-6)(H2O)3]Fe(CN)6·2H2O, where X = Eu and Dy (materials 2a and 2b, respectively), in response to heat, light, and electron beam exposure. We employ correlative light–electron microscopy using transmission electron microscopy (TEM) finder grids to accurately image and sense spin–spin interacting particles down to the single-particle level. We used surface-sensitive optically detected magnetic resonance (ODMR) and magnetic modulation (MM) of FND photoluminescence (PL) to sense spins to a distance of ca. 10–30 nm. We show that ODMR and MM sensing was not sensitive to the temperature-induced SCO of FeII in 1 as formation of paramagnetic FeIII through surface oxidation (detected by X-ray photoelectron spectroscopy) on heating obscured the signal of bulk SCO switching. We found that proximal FNDs could effectively sense the chemical transformations induced by the 200 keV electron beam in 1, namely, AgI → Ag0 and FeII → FeIII. However, transformations induced by the electron beam are irreversible as they substantially disrupt the structure of MOF particles. Finally, we demonstrate NV– sensing of reversible photomagnetic switching, FeIII + (18-crown-6) ⇆ FeII + (18-crown-6)+ •, triggered in 2a and 2b by 405 nm light. The photoredox process of 2a and 2b proved to be the best candidate for room-temperature single-particle magnetic switching utilizing FNDs as a sensor, which could have applications into next-generation quantum technologies.

KW - spin-crossover

KW - Nitrogen-vacancy sensing

KW - metal−organic framework

KW - nanodiamond

KW - transmission electron microscopy

KW - photomagnetism

U2 - 10.1021/acsnano.3c11820

DO - 10.1021/acsnano.3c11820

M3 - Article

SN - 1936-0851

VL - 18

SP - 7148

EP - 7160

JO - ACS Nano

JF - ACS Nano

IS - 9

ER -

Sensing the Spin State of Room-Temperature Switchable Cyanometallate Frameworks with Nitrogen-Vacancy Centers in Nanodiamonds

Abstract

Bibliographical note

Keywords

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