Design of magneto-plasmonicheterostructures formed by Au decorated on

magnetic Prussian Blue-type nanocrystals

Roger Sanchis Gual

Instituto de Ciencia Molecular

Small Chem 2021 Online International Conference

17/02/2021

Prussian Blue Analogue (PBA)

1

MII and MIII = transition metal A = alkali cation

• Chemical versatility• Tunability of the properties• Optical transparency• Charge transfer properties• Magnetic properties

AaMb[M’(CN)6]c·nH2O

Prussian Blue Analogue (PBA)

1

MII and MIII = transition metal A = alkali cation

• Chemical versatility• Tunability of the properties• Optical transparency• Charge transfer properties• Magnetic properties

AaMb[M’(CN)6]c·nH2O

PBAs have potential used in magneto-optical devices

Magneto-optical effects are usually weak

Magneto-optics are based on the interaction between the light and

magnetically ordered materials

Main problem

Magneto-plasmonics

2ACS Appl. Mater. Interfaces 2013, 5, 1955−1960

Ferromagnetic material

Plasmonic material

Large MO activity but broad and weak plasmon resonances

Important plasmon resonances but too low MO activity

Fair plasmon resonances and large enough MO activity

Magneto-plasmonics

2

Magneto-plasmonic materials are heterostructures where ferromagnetic and plasmonic structures are combined in a unique entity

ACS Appl. Mater. Interfaces 2013, 5, 1955−1960

Ferromagnetic material

Plasmonic material

Large MO activity but broad and weak plasmon resonances

Important plasmon resonances but too low MO activity

Fair plasmon resonances and large enough MO activity

Au-PBA heterostructures

3

100 nm

Chem. Eur. J. 2017, 23, 7483 – 7496 Anal. Chem. 2017, 89, 1551−1557

Due to the synthetic routes, thesehybrids are restricted to weak

magnetic PBAs and isotropic Au cores

Anal. Chim. Acta 2012, 711 40– 45

TC = 2 K

TC = 5 K

TC = 5 K

Synthetic protocol

50 nm

50 nm

4

Synthetic protocol

50 nm

50 nm

4No interaction

100 nm

4000 3000 2000 1000

νO-H

νC-O-C

νC-H

Tran

smitt

ance

/ a.

u.

Wavelength / cm-1

Au@Citrate Au@HS-PEG-NH2

νC=O

Synthetic protocol

0 1 2 3 4 5 6 7 8-10

0

10

20

30

40

ζ-po

tent

ial /

mV

pH 5

NPζ-potential / mV

Citrate CTAB HS-PEG-NH2Au NPs -40 ± 6 / 9 ± 6Au NRs / 35 ± 7 12 ± 4Au NSs / / 12 ± 4Ag NPs -35 ± 2 / 11 ± 5

Synthetic protocol

6

pH 2-3 pH 3-5

Edge:M(CN)63- surroundedby 4 metallic centers

Face:M(CN)63- surroundedby 5 metallic centers

Larger negative charge density on (and near) the edges than on their faces

7Higher interaction with the amino group

Synthetic protocol

-2000 -1000 0 1000 2000-80

-40

0

40

80

-100 0 100

-5

0

5

Au-PBA PBA

M /

emu·

g-1

H / Oe

2K

Magnetic properties

0 20 40 60 80 1000

20

40

60

80 Au-PBA PBA

M /

emu·

g-1

T / K

The magnetic properties of the hybrid are almost identical to those measured for pristine NiCr PBA NPs

8

Plasmonic properties

400 500 600 700 800 9000.0

0.4

0.8

1.2

1.6

500 550

0.5

0.9

Abso

rban

ce

λ / nm

Au Au-PBA(random) Au-PBA(edges) PBA

400 500 600 700 800 9000.0

0.2

0.4

0.6

0.8

1.0

480 520 560

0.6

0.8

Abso

rban

ceλ / nm

Au Au-PBA PBA

Δλ = 6 nm Δλ = 0 nm

Modification of the local refractive index at the surface of the Au NPsPlasmon

shift9

10

400 500 600 700 800 9000,0

0,4

0,8

1,2

500 550

0,5

0,9

Abso

rban

ce

λ / nm

Au Au-PBA PBA

400 500 600 700 800 9000.0

0.5

1.0

600 750

0.5

0.6

0.7

Abso

rban

ce

λ / nm

Au Au-PBA PBA

400 500 600 700 800 9000

1

2

800 900

1

2

Abso

rban

ce

λ / nm

Au Au-PBA PBA

100 nm100 nm

Au NRs Au NSs

300 400 500 600 700 8000.0

0.4

0.8

1.2

400 450

0.5

0.8

1.1

Abso

rban

ce

λ / nm

Ag Ag-PBA PBA

100 nm

Ag NPs

100 nm

Au NPs

It is possible to tune the plasmonic properties of the hybrids in the whole visible spectrum

Synthesis versatility

11

Synthesis versatility

100 nm 400 nm100 nm

12

400 500 600 700 800 9000.0

1.0

2.0

3.0

Abso

rban

ce

λ / nm

Au Au-PB PB

100 nm

400 500 600 700 800 9000.0

0.5

1.0

1.5

Abso

rban

ce

λ / nm

Au Au-PBA PBA

100 nm

400 500 600 700 800 9000.0

0.5

1.0

1.5

Abso

rban

ce

λ / nm

Au Au-PBA PBA

200 nm

Synthesis versatility

400 500 600 700 800 9000.0

0.4

0.8

1.2

Abso

rban

ce

λ / nm

Au Au-PBA PBA

100 nm

Conclusions

13

This synthetic procedure permits to prepare hybrid magneto-plasmonic

nanostructures formed by metallic NPs decorating PBA.

We can control the location of the metallic NPs on the PBA: randomly

over the whole cubic surface or preferentially on the edges.

It is possible to anchor anisotropic metallic NPs allowing to tune the

optical properties in a wide range of the visible spectrum.

It provides a versatile platform to investigate the enhancement of the

magneto-optical properties thanks to the coupling with the plasmons.

"The design of magneto-plasmonic nanostructures formed by magnetic Prussian Blue-typenanocrystals decorated with Au nanoparticles" Chem. Comm. 2021

Thanks for your attention!

University of Valencia

Isidora Susic

Ramón Torres-Cavanillas

Dr. Marc Coronado-Puchau

Prof. Eugenio Coronado

Acknowledgments

University of Antwerp

Dr. Daniel Arenas-Esteban

Prof. Sara Bals

Universitey of Paris-Saclay

Prof. Talal Mallah

Design of magneto-plasmonic heterostructures formed by Au decorated on

magnetic Prussian Blue-type nanocrystals

Roger Sanchis Gual

Instituto de Ciencia Molecular

Small Chem 2021 Online International Conference

17/02/2021

Supporting: AuNRs decoration

Supporting: Au decoration

Supporting: Au/PBA molar ratio

0.31:1 0.40:1 0.50:1

0.28:1 0.41:1 1.12:1

Stability characterization

10 20 30 40 50

(2 0

0)

Inte

nsity

/ a.

u.2θ / º

Au-PBA PBA

(1 1

1)

400 500 600 700 800 9000.0

0.2

0.4

0.6

0.8

1.0

Abso

rban

ce

λ / nm

0 min 10 min 60 min 90 min 120 min 3h 24h 48h

8

Aggregation of the heterostructure occurs with time

Design of magneto-plasmonic heterostructures formed by Au decorated on magnetic Prussian Blue-type nanocrystalsNúmero de diapositiva 2Número de diapositiva 3Número de diapositiva 4Número de diapositiva 5Número de diapositiva 6Número de diapositiva 7Número de diapositiva 8Número de diapositiva 9Número de diapositiva 10Número de diapositiva 11Número de diapositiva 12Número de diapositiva 13Número de diapositiva 14Número de diapositiva 15Número de diapositiva 16Número de diapositiva 17Número de diapositiva 18Design of magneto-plasmonic heterostructures formed by Au decorated on magnetic Prussian Blue-type nanocrystalsNúmero de diapositiva 20Número de diapositiva 21Número de diapositiva 22Número de diapositiva 23