Chiral thin films showing electronic and plasmonic circular dichroism (CD) are intensively explored for optoelectronic applications. The most studied chiral organic films are the composites exhibiting a helical geometry, which often causes entanglement of circular optical properties with unwanted linear optical effects (linearly polarized absorption or refraction). This entanglement limits tunability and often translates to a complex optical response. This paper describes chiral films based on dark conglomerate, sponge-like, liquid crystal films, which go beyond the usual helical type geometry, waiving the problem of linear contributions to chiroptical electronic and plasmonic properties. First, we show that purely organic films exhibit high electronic CD and circular birefringence, as studied in detail using Mueller matrix polarimetry. Analogous linear properties are two orders of magnitude lower, highlighting the benefits of using the bi-isotropic dark conglomerate liquid crystal for chiroptical purposes. Next, we show that the liquid crystal can act as a template to guide the assembly of chemically compatible gold nanoparticles into 3D spiral-like assemblies. The Mueller matrix polarimetry measurements confirm that these composites exhibit both electronic and plasmonic circular dichroisms, while nanoparticle presence is not compromising the beneficial optical properties of the matrix.
REFERENCES
1.
H.
Chen
, W.
Wu
, J.
Zhu
, Z.
Yang
, W.
Gong
, W.
Gao
, S. A.
Yang
, and L.
Zhang
, “Chiral phonon diode effect in chiral crystals
,” Nano Lett.
22
(4
), 1688
–1693
(2022
).2.
D.
Liu
, H.
Li
, R.
Han
, H.
Liu
, and S.
Zang
, “Multiple stimuli‐responsive luminescent chiral hybrid antimony chlorides for anti‐counterfeiting and encryption applications
,” Angew. Chem.
135
, 36
(2023
).3.
P.
Lv
, X.
Lu
, L.
Wang
, and W.
Feng
, “Nanocellulose‐based functional materials: From chiral photonics to soft actuator and energy storage
,” Adv. Funct. Mater.
31
(45
), 2104991
(2021
).4.
Y.-H.
Kim
, Y.
Zhai
, H.
Lu
, X.
Pan
, C.
Xiao
, E. A.
Gaulding
, S. P.
Harvey
, J. J.
Berry
, Z. V.
Vardeny
, J. M.
Luther
, and M. C.
Beard
, “Chiral-induced spin selectivity enables a room-temperature spin light-emitting diode
,” Science
371
, 1129
–1133
(2021
).5.
Z.
Huang
, Z.
He
, B.
Ding
, H.
Tian
, and X.
Ma
, “Photoprogrammable circularly polarized phosphorescence switching of chiral helical polyacetylene thin films
,” Nat. Commun.
13
(1
), 7841
(2022
).6.
X.
Wang
, Q.
Wang
, X.
Zhang
, J.
Miao
, J.
Cheng
, T.
He
, Y.
Li
, Z.
Tang
, and R.
Chen
, “Circularly polarized light Source from self‐assembled hybrid nanoarchitecture
,” Adv. Opt. Mater.
10
(16
), 2200761
(2022
).7.
J.
Wade
, J. N.
Hilfiker
, J. R.
Brandt
, L.
Liirò-Peluso
, L.
Wan
, X.
Shi
, F.
Salerno
, S. T. J.
Ryan
, S.
Schöche
, O.
Arteaga
, T.
Jávorfi
, G.
Siligardi
, C.
Wang
, D. B.
Amabilino
, P. H.
Beton
, A. J.
Campbell
, and M. J.
Fuchter
, “Natural optical activity as the origin of the large chiroptical properties in π-conjugated polymer thin films
,” Nat. Commun.
11
(1
), 6137
(2020
).8.
M.
Morgenroth
, M.
Scholz
, T.
Lenzer
, and K.
Oum
, “Ultrafast UV–Vis transient absorption and circular dichroism spectroscopy of a polyfluorene copolymer showing large chiral induction
,” J. Phys. Chem. C
124
(18
), 10192
–10200
(2020
).9.
D. K.
Yoon
, Y.
Yi
, Y.
Shen
, E. D.
Korblova
, D. M.
Walba
, I. I.
Smalyukh
, and N. A.
Clark
, “Orientation of a helical nanofilament (B4) liquid-crystal phase: Topographic control of confinement, shear flow, and temperature gradients
,” Adv. Mater.
23
(17
), 1962
–1967
(2011
).10.
A.
Abbasi Moud
, “Chiral liquid crystalline properties of cellulose nanocrystals: Fundamentals and applications
,” ACS Omega
7
(35
), 30673
–30699
(2022
).11.
G.
Zhang
, X.
Cheng
, Y.
Wang
, and W.
Zhang
, “Supramolecular chiral polymeric aggregates: Construction and applications
,” Aggregate
4
(1
), e262
(2023
).12.
J. P.
Joseph
, S. R.
Abraham
, A.
Dutta
, A.
Baev
, M. T.
Swihart
, and P. N.
Prasad
, “Modulating the chiroptical response of chiral polymers with extended conjugation within the structural building blocks
,” J. Phys. Chem. Lett.
13
(39
), 9085
–9095
(2022
).13.
Y.
Yao
, T. J.
Ugras
, T.
Meyer
, M.
Dykes
, D.
Wang
, A.
Arbe
, S.
Bals
, B.
Kahr
, and R. D.
Robinson
, “Extracting pure circular dichroism from hierarchically structured CdS magic cluster films
,” ACS Nano
16
(12
), 20457
–20469
(2022
).14.
A.
Taddeucci
, F.
Zinna
, G.
Siligardi
, and L.
Di Bari
, “Circularly polarized microscopy of thin films of chiral organic dyes
,” Chem. Biomed. Imaging
1
(5
), 471
–478
(2023
).15.
N.
Berova
, K.
Nakanishi
, and R.
Woody
, Circular Dichroism: Principles and Applications
, 2nd ed. (Wiley-VCH
, New York
, 2000
).16.
A.
Rodger
and B.
Nordén
, Circular Dichroism and Linear Dichroism
(Oxford University Press
, Oxford, New York
, 1997
).17.
M.
Salamończyk
, N.
Vaupotič
, D.
Pociecha
, R.
Walker
, J. M. D.
Storey
, C. T.
Imrie
, C.
Wang
, C.
Zhu
, and E.
Gorecka
, “Multi-level chirality in liquid crystals formed by achiral molecules
,” Nat. Commun.
10
, 1922
(2019
).18.
L. E.
Hough
, H. T.
Jung
, D.
Krüerke
, M. S.
Heberling
, M.
Nakata
, C. D.
Jones
, D.
Chen
, D. R.
Link
, J.
Zasadzinski
, G.
Heppke
, J. P.
Rabe
, W.
Stocker
, E.
Körblova
, D. M.
Walba
, M. A.
Glaser
, and N. A.
Clark
, “Helical nanofilament phases
,” Science
325
(5939
), 456
–460
(2009
).19.
L.
Wang
, A. M.
Urbas
, and Q.
Li
, “Nature-inspired emerging chiral liquid crystal nanostructures: From molecular self-assembly to DNA mesophase and nanocolloids
,” Adv. Mater.
32
, 1801335
(2018
).20.
P.
Szustakiewicz
, N.
Kowalska
, D.
Grzelak
, T.
Narushima
, M.
Góra
, M.
Bagiński
, D.
Pociecha
, H.
Okamoto
, L. M.
Liz-Marzán
, and W.
Lewandowski
, “Supramolecular chirality synchronization in thin films of plasmonic nanocomposites
,” ACS Nano
14
(10
), 12918
–12928
(2020
).21.
W.
Park
and D. K.
Yoon
, “Orientation control of helical nanofilament phase and its chiroptical applications
,” Crystals
10
(8
), 675
(2020
).22.
W.
Wu
and M.
Pauly
, “Chiral plasmonic nanostructures: Recent advances in their synthesis and applications
,” Mater. Adv.
3
(1
), 186
–215
(2022
).23.
D.
Vila-Liarte
, N. A.
Kotov
, and L. M.
Liz-Marzán
, “Template-assisted self-assembly of achiral plasmonic nanoparticles into chiral structures
,” Chem. Sci.
13
(3
), 595
–610
(2022
).24.
J.
Mendoza‐Carreño
, P.
Molet
, C.
Otero‐Martínez
, M. I.
Alonso
, L.
Polavarapu
, and A.
Mihi
, “Nanoimprinted 2D‐chiral perovskite nanocrystal metasurfaces for circularly polarized photoluminescence
,” Adv. Mater.
35
, 2210477
(2023
).25.
D.
Château
, S.
David
, G.
Berginc
, C.
Lopes
, F.
Chaput
, F.
Lerouge
, A.
Désert
, C.
Andraud
, and S.
Parola
, “Plasmonic bipyramidal Au nanoparticles enhance near-infrared nonlinear absorption of dyes confined in sol–gel materials: Implications for the safe utilization of lasers
,” ACS Appl. Nano Mater.
5
(3
), 3773
–3780
(2022
).26.
M.
Bagiński
, M.
Tupikowska
, G.
González‐Rubio
, M.
Wójcik
, and W.
Lewandowski
, “Shaping liquid crystals with gold nanoparticles: Helical assemblies with tunable and hierarchical structures via thin‐film cooperative interactions
,” Adv. Mater.
32
(1
), 1904581
(2020
).27.
D.
Grzelak
, M.
Tupikowska
, D.
Vila‐Liarte
, D.
Beutel
, M.
Bagiński
, S.
Parzyszek
, M.
Góra
, C.
Rockstuhl
, L. M.
Liz‐Marzán
, and W.
Lewandowski
, “Liquid crystal templated chiral plasmonic films with dynamic tunability and moldability
,” Adv. Funct. Mater.
32
(16
), 2111280
(2022
).28.
S.
Parzyszek
, J.
Tessarolo
, A.
Pedrazo-Tardajos
, A. M.
Ortuño
, M.
Bagiński
, S.
Bals
, G. H.
Clever
, and W.
Lewandowski
, “Tunable circularly polarized luminescence via chirality induction and energy transfer from organic films to semiconductor nanocrystals
,” ACS Nano
16
, 18472
–18482
(2022
).29.
M.
Lipok
, P.
Obstarczyk
, S.
Parzyszek
, Y.
Wang
, M.
Bagiński
, T.
Buergi
, W.
Lewandowski
, and J.
Olesiak‐Bańska
, “Circularly polarized luminescence from atomically precise gold nanoclusters helically assembled by liquid‐crystal template
,” Adv. Opt. Mater.
11
(3
), 2201984
(2023
).30.
L. E.
Hough
et al, “Chiral isotropic liquids from achiral molecules
,” Science
325
, 452
–456
(2009
).31.
J. L.
Pezzaniti
, “Mueller matrix imaging polarimetry
,” Opt. Eng.
34
(6
), 1558
(1995
).32.
R.
Hussain
, T.
Jávorfi
, and G.
Siligardi
, “CD imaging at high spatial resolution at diamond B23 beamline: Evolution and applications
,” Front. Chem.
9
, 616928
(2021
).33.
H.
Sasaki
, Y.
Takanishi
, J.
Yamamoto
, and A.
Yoshizawa
, “Achiral flexible liquid crystal trimers exhibiting chiral conglomerates
,” trimers exhibiting chiral conglomerates
12
(14
), 3331
–3339
(2016
).34.
H.
Sasaki
, Y.
Takanishi
, J.
Yamamoto
and A.
Yoshizawa
, “Achiral flexible liquid crystal trimers exhibiting gyroid-like surfaces in chiral conglomerate phases
,” Soft Matter
12
(37
), 6521
–6528
(2017
).35.
S. B. G.
Blanquer
, M.
Werner
, M.
Hannula
, S.
Sharifi
, G. P. R.
Lajoinie
, D.
Eglin
, J.
Hyttinen
, A. A.
Poot
, and D. W.
Grijpma
, “Surface curvature in triply-periodic minimal surface architectures as a distinct design parameter in preparing advanced tissue engineering scaffolds
,” Biofabrication
9
(2
), 025001
(2017
).36.
G.
Albano
et al, “Chiroptical properties in thin films of π-conjugated systems
,” Chem. Rev.
120
(18
), 10145
–10243
(2020
).37.
M.
Schulz
, M.
Mack
, O.
Kolloge
, A.
Lutzen
, and M.
Schiek
, “Organic photodiodes from homochirall-proline derived squaraine compounds with strong circular dichroism
,” Phys. Chem. Chem. Phys.
19
, 6996
–7008
(2017
).38.
D.
Keller
and C.
Bustamante
, “Theory of the interaction of light with large inhomogeneous molecular aggregates. II. Psi-type circular dichroism
,” J. Chem. Phys.
84
, 2972
–2980
(1986
).39.
V. A.
Kuznetsova
, E.
Mates-Torres
, N.
Prochukhan
, M.
Marcastel
, F.
Purcell-Milton
, J.
O’Brien
, A. K.
Visheratina
, M.
Martinez-Carmona
, Y.
Gromova
, M.
Garcia-Melchor
, and Y. K.
Gun’ko
, “Effect of chiral ligand concentration and binding mode on chiroptical activity of CdSe/CdS quantum dots
,” ACS Nano
13
(11
), 13560
–13572
(2019
).40.
M.
Kurata
and A.
Yoshizawa
, “The formation of a chiral supramolecular structure acting as a template for chirality transfer
,” Chem. Commun.
56
(59
), 8289
–8292
(2020
).41.
Y.
Zheng
, X.
Zhong
, Z.
Li
, and Y.
Xia
, “Successive, seed‐mediated growth for the synthesis of single‐crystal gold nanospheres with uniform diameters controlled in the range of 5–150 nm
,” Part. Part. Syst. Charact.
31
, 266
–273
(2014
).42.
G.
González-Rubio
, V.
Kumar
, P.
Llombart
, P.
Díaz-Núñez
, E.
Bladt
, T.
Altantzis
, S.
Bals
, O.
Peña-Rodríguez
, E. G.
Noya
, L. G.
Macdowell
, A.
Guerrero-Martínez
, and L. M.
Liz-Marzán
, “Disconnecting symmetry breaking from seeded growth for the reproducible synthesis of high quality gold nanorods
,” ACS Nano
13
(4
), 4424
–4435
(2019
).43.
Y.
Chen
and X.
Wang
, “Novel phase-transfer preparation of monodisperse silver and gold nanoparticles at room temperature
,” Mater. Lett.
62
(15
), 2215
–2218
(2008
).44.
G.
Albano
, M.
Górecki
, G.
Pescitelli
, L.
Di Bari
, T.
Jávorfi
, R.
Hussain
, and G.
Siligardi
, “Electronic circular dichroism imaging (CDi) maps local aggregation modes in thin films of chiral oligothiophenes
,” New J. Chem.
43
(36
), 14584
–14593
(2019
).© 2024 Author(s). Published under an exclusive license by AIP Publishing.
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