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Rationalizing the design and implementation of chiral hybrid perovskites
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Review
Rationalizing the design and implementation
of chiral hybrid perovskites
Adriana Pietropaolo,1,* Alessandro Mattoni,2,* Giovanni Pica,3 Mariagrazia Fortino,1
Gioacchino Schifino,1 and Giulia Grancini3,*
SUMMARY The bigger picture

Molecular asymmetry occurs at all scales in nature, spanning organic Chiral hybrid perovskites have
to inorganic frameworks with consequences of high significance. For recently emerged as a relevant
this reason, asymmetric organic and inorganic materials are inces- class of asymmetric materials
santly gaining considerable interest owing to the opportunity of because of their prominent
reaching tunable chiral signatures. In recent years, the chiral hybrid circularly polarized emission,
organic-inorganic perovskites in which the chiral organic ligands together with their interesting
usually induce the symmetry breaking are receiving growing atten- ferroelectric and chiral spintronics
tion. Their circularly polarized emissions without the need for features. Indeed, the choice of the
expensive ferromagnets or extremely low temperatures are chiral organic ligand is not
appealing features for the industry. Until now, there has been no straightforward and impacts the
clear relationship between the structure of the chiral perovskites efficiency of chiral transfer to the
and the generated signal. This review aims at focusing on the supra- inorganic perovskite. Molecular
molecular chiral amplification mechanisms in asymmetric perov- rotations of the organic ligand
skites, rationalizing how to enhance their chiral emission signatures. leading to axial chirality can be
We conclude by broadening our view toward future challenges in exploited in this context,
exploring modern simulation protocols to optimize the design of although, to date, it is a strategy
chiral hybrid perovskites. largely unexplored. Furthermore,
modern multiscale modeling and
simulations nowadays have an
INTRODUCTION
unprecedented level of accuracy,
How molecular chirality originates on earth is still a matter of debate, with conse- enabling an efficient chiral design
quences of high relevance.1 Chirality is a property of asymmetry and refers to the of these kinds of materials. The
phenomenon that a system cannot overlap with its mirror image, and therefore it aim of this review is to discuss and
is distinguishable from it. In three dimensions, every structure that lacks a mirror predict novel design concepts for
plane of symmetry (S1), an inversion center of symmetry (S2), or a higher improper chiral hybrid perovskites,
rotation (rotoreflection) Sn axis of symmetry is chiral. A comprehensive classification particularly given the emerging
of the chiral lattices and space groups is reported in the study conducted by Long tools of computational chemistry.
et al.2 The symmetry breaking of the mirror planes, inversion centers, or Sn rotore-
flection operations entails highly different outcomes of the reflected molecular im-
ages, termed enantiomers. This simple property can be exploited in many areas of
science, such as biology, spintronics, quantum communication, and chiroptoelec-
tronics including circularly polarized light (CPL) photodetectors and light sour-
ces.2–4 These observations have led to a growing interest toward asymmetric mate-
rials since the opportunity of tunable chiral properties at variable scale. Chiral
materials can indeed exhibit circular dichroism (CD),5 ferroelectricity,6 and quantum
properties.7 Among the network of chiral materials, inorganic building blocks have
recently shown interesting luminescent, electrical, or magnetic properties, particu-
larly when combined with chiral organic ligands. In this context, the chiral hybrid
organic-inorganic perovskites (HOIPs) are appealing frameworks for chiroptoelec-
tronic applications as three-dimensional displays, bioencoding as well as tomogra-
phy.8 Synthesis of chiral perovskites using chiral ligands were first demonstrated in
Chem 8, 1–23, May 12, 2022 ª 2022 Elsevier Inc. 1

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Review
20039 and 200610 for 1D and 2D chiral-perovskite single crystals, respectively. Chiral
perovskites re-emerged in 20175,11 when the first chiroptical study was performed
and soon after spearheaded contributions are continuously showing their prominent
chiral signatures.2,6,8,12–15 More recently, since 2019, chiral HOIPs have been further
explored. Examples include 1D15 and 2D16 chiral perovskite ferroelectrics, circularly
polarized photodetectors based on 1D4 and 2D,17 chiral perovskites, and two-
photon absorption-based upconverted circularly polarized luminescence.18 Exam-
ples of chiral perovskites are represented in Figure 1 and can be designed by incor-
porating chiral organic molecules into the perovskite framework, inducing chirality
to the whole system. Distortions that often stabilize the perovskite lattice may cause
a reduction in symmetry. The chiral molecular bias has also a tremendous impact on
the generation of the asymmetric scaffold of inorganic perovskites. Indeed, the
intense research efforts devoted to elucidate the nature of the luminescence effi-
ciency of the chiral perovskites will generate increased knowledge on the mecha-
nism of their chiral amplification.
This review discusses the actual experimental achievements and simulation advances
connected to the mechanisms of chiral amplification in chiral HOIPs, to pursue an
enhancement in their chiral signatures. We analyze advances and drawbacks in the
realization of chiral perovskites and their applications, thereby examining whether
the mechanisms of supramolecular chirality in organic assemblies can be projected
for explaining the asymmetry in chiral HOIPs. We will consider the coupling of thermal
fluctuations with light irradiation, which can possibly affect the asymmetry of transition
states, enabling a set of chiral conformations with specific chiral signatures. We will
then describe modern chemical simulation frameworks as a flywheel for bringing forth-
coming design concepts for the chiral chemical design, with an increased knowledge
on the mechanism of their chiral amplification, which can be directly projected toward
the realization of ‘‘à la carte’’ chiral chemical design. This would be a formidable
achievement and can be reachable by combining the most advanced chiroptical tech-
niques with well-tailored modern chemical simulations.
BACKGROUND ON HYBRID ORGANIC-INORGANIC PEROVSKITES

The term ‘‘perovskites’’ indicates a group of materials with analogous chemical struc-
ture, related to a specific mineral discovered in 1839 by Gustav Rose (calcium tita-
nate CaTiO3). Thus, the basic structure of a perovskite is described by the general-
ized formula ABX3, where A indicates a cation with large ionic radius (usually
methylammonium MA+, formamidinium FA+, or combination of them), B a divalent
metallic cation with short ionic radius (Sn2+ or Pb2+), and X a halide anion (I, Cl,
Br). The ions B and X form octahedra, in which the former takes place in the center
and the halides in the corners around B, whereas the cation A places itself between
the octahedra, rebalancing the charge of the crystal structure.
Typically, the symmetry of the unit cell varies with temperature, being rombohedric,
orthorhombic, tetragonal, or cubic, but some distortions may occur (e.g., due to the 1Dipartimento di Scienze della Salute, Università
movement of the B cation from the center position in the octahedra or to the dimen- di Catanzaro, Viale Europa, 88100 Catanzaro, Italy
2Istituto Officina deiMateriali (CNR-IOM), sede di
sion of the cations that prevents it from perfectly fitting into the structure). In order to
Cagliari, Cittadella Universitaria, I-09042
quantify the extent of this distortion, the Goldschmidt tolerance factor t was defined: Monserrato (CA), Italy
rA + rB 3Dipartimento di Chimica and INSTM, Università
t = pffiffiffi di Pavia, Via T. Taramelli 14, 27100 Pavia, Italy
2ðrB + rX Þ
*Correspondence: apietropaolo@unicz.it (A.P.),
mattoni@iom.cnr.it (A.M.),
where rA, rB, and rX are the radii of the A and B cations and X anions, respectively. For giulia.grancini@unipv.it (G.G.)
stable crystals, this factor ranges between 0.7 and 1, the latter corresponding to a https://doi.org/10.1016/j.chempr.2022.01.014
2 Chem 8, 1–23, May 12, 2022

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Review
Figure 1. Examples of chiral halide perovskites

(A) 1D chiral hybrid perovskite. Reprinted with permission from Chen et al. 4 Copyright ª 2019, Springer Nature Limited.
(B) 2D chiral hybrid perovskite with a 2:1 ligand/perovskite ratio. Reprinted with permission from Long et al. 2 Copyright ª 2020, Springer Nature Limited.
(C) 3D chiral hybrid perovskite. Reprinted with permission from Long et al. 19 Copyright 2019 John Wiley & Sons.
structure without distortions. Indeed, the tolerance factor is an empirical formula

fitting a wide number of perovskites structures, despite some of them such as
a-FAPbI3 and a-CsPbI3 for which it fails to predict stability.20
Apart from the 3D structures of perovskites, the 2D perovskites are generally

described with a formula (A0 )m(A)n 1BnX3n + 1, where A0 indicates a divalent (m =
1) or monovalent (m = 2) cation forming a bilayer or monolayer connecting the inor-
ganic (A)n 1BnX3n + 1 2D sheets, and n indicates the layer thickness of metal halide
sheets, where Ruddlesen-Popper (RP), Dion-Jacobson (DJ), and the alternating cat-
ions in the interlayers (ACI) are the most common phases (Figure 2).21–23 Low-dimen-
sional 1D perovskites, until now, have been appreciably less investigated with
respect to 2D and 3D perovskites. In 1D perovskites, the metal halide octahedral
moiety can be corner-sharing, edge-sharing, or face-sharing leading to 1D nano-
wire, surrounded by organic cations.24 The whole configuration may have both a
linear and a zigzag orientation. It is worth mentioning that there is no unique chem-
ical formula for 1D perovskites; indeed, it can vary depending on the connecting
methods and the organic cations involved. Low-dimensional perovskites have, how-
ever, the drawbacks of their wide optical band gap and limited charge transport, two
conditions unfavorable for photovoltaic devices. Indeed, 3D systems represent one
of the challenges for the chiral perovskites that can have an enormous impact on
non-volatile memories or ferroelectric chiral devices. However, the harsh conditions
of the synthesis caused by the poor number of compatible organic cations (accord-
ing to the tolerance constraints) are hampering, until now, a straightforward design
strategy for the 3D systems. The synthesis of HOIP can be performed in the form of
thin films, microcrystals, nanocrystals, and quantum dots (QDs). Films are fabricated
in a single- or two-step deposition from solutions of their precursor salts (MAX, FAX,
and PbX2, where MA, FA, and X stand for methylammonium, formamidinium and a
generic halide, respectively) dissolved in solvents such as dimethyl-formamide
(DMF) or dimethyl sulfoxide (DMSO). Other methods for the preparation of films
include antisolvent-assisted deposition,25 vacuum- and gas-pumping,26 and hot-
casting.27 Single crystals of 3D halide perovskites are fabricated through inverse
temperature crystallization or antisolvent vapor-assisted crystallization methods,
whereas temperature lowering method is adopted for 2D, quasi-2D, and 1D chiral
perovskites.28 Finally, perovskite nanocrystals are prepared by the hot-injection29
or ligand-assisted reprecipitation30 methods, which exploit surface capping using
Chem 8, 1–23, May 12, 2022 3

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Figure 2. Schematic representation of 2D perovskite structures and their applications

(A) Optoelectronic applications for 2D perovskites. Adapted and reprinted with permission from
Zhang et al. 21 Copyright 2020 Royal Society of Chemistry.
(B and C) Ruddlesen-Popper, Dion-Jacobson and the alternating cations in the interlayers phases
of 2D perovskite structures. (B) Ca 4 Mn 3 O 10 (left) and (BA) 2 (MA) 2 Pb 3 I 10 (n = 3; right); (C)
CsBa 2 Ta 3 O 10 (left) and (3amp)(MA)2 Pb3 I 10 (n = 3; right). Reprinted with permission from Mao et al. 22
Copyright 2018, American Chemical Society.
(D) (Gua)(MA) n Pb n I 3n+1 (n = 1, 2, 3). Reprinted with permission from Soe et al. 23 Copyright 2017,
American Chemical Society. AMP, 3-(aminomethyl)piperidinium; Gua, guanidinium cation; MA,
methylammonium cation.
long-chain organic ligands whose length, together with reaction temperature,

determine the size and morphology of nanocrystals and QDs. Due to their high ab-
sorption coefficients, long diffusion lengths of charge carriers, and low exciton-bind-
ing energies, perovskites are the best candidates to be utilized as active material in
solar cells. The first solar cell exploiting this kind of material,31 which substituted dye
in a dye-sensitized solar cell, showed a power conversion efficiency (PCE) of 3.8%,
and subsequent studies32 used a solid-state MAPbI3 obtaining a PCE exceeding
10%. In addition to the properties already mentioned, the tunability of the photolu-
minescence (PL) emission and the high photoluminescence quantum yield (PLQY)
make perovskite an excellent candidate to be utilized in light-emitting diodes
(LEDs), in which a current flow in the device leads to the emission of light in the visible
region. Furthermore, the PL color of these perovskites is tuned in the visible region
through the preparation of mixed halide perovskites or post-synthesis halide ex-
change reactions. Depending on the halide anion inside the perovskite structure,
the PL emission can range from blue (pure chloride perovskite), green (bromide
perovskite) to red (iodide perovskite). The PL color can then be tuned between
blue and green by increasing the proportion of bromide in chloride perovskites or
chloride in bromide perovskites. Similarly, by mixing bromide and iodide ions the
4 Chem 8, 1–23, May 12, 2022

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Review
PL color can be tuned between green and red. The capability of the hybrid perov-
skite structure to easily accommodate a wide variety of ions led to the possibility
of enabling HOIPs to exhibit a wide variety of properties such as ferroelectricity,
magnetism, as well as chirality. Recent studies demonstrate that the chirality-
induced spin selectivity (CISS) effect manifests, highlighting the utility of chiral-
HOIP materials for chiral opto-spintronic applications.33 In addition, the observation
of the circular photogalvanic effect (CPGE)—an optoelectronic phenomenon associ-
ated with the spin-orbit coupling (SOC) of heavy atoms in noncentrosymmetric sys-
tems—in 2D HOIPs make them a promising platform for engineering opto-spin-
tronic functionalities.34 Furthermore, spin-dependent photovoltaic and
photogalvanic responses of optoelectronic devices, based on chiral 2D HOIPs,
have been observed.35 Among this huge variety of possible applications, chiroptics
and chiral spintronics are discussed in more detail in the following section.
CHIRAL HYBRID ORGANIC-INORGANIC PEROVSKITES: DESIGN

STRATEGIES BY TOPOLOGICAL CHIRALITY
Chiral perovskites belong to a particular class of HOIPs, featured by a structural
asymmetry. There are two main design strategies to obtain chiral perovskites here-
after named (1) the ligands and (2) environment. The ligands strategy exploits the
chiral distortion of the perovskite induced by chiral organic molecules as ligands
(that is the case of the first chiral hybrid perovskite reported in the study conducted
by Billing and Lemmerer9 and of its 2D counterpart). The environment strategy uses
the chiral environment generating a helical arrangement, induced from distorted
chiral perovskite structures, through self-assembling or with a surface deposition
of a chiral source. A further list of the design strategies is provided in the study con-
ducted by Long et al.2 Most of the chiral perovskites synthetized so far have adopted
the ligand strategy, where the chirality transfer is often generated through the inclu-
sion of a chiral substituent, inducing a chiral amplification to high-dimension chiral
hybrid networks.13 To date, the stereocenter chirality of the ligand having four
different substituents of a quaternary carbon is the source of asymmetry widely intro-
duced in the chiral HOIPs. Chiral ligands as a-methylbenzylamine (MBA),36 for which
the synonym 1-phenylethylamine (a-PEA) was also used,4 or a-methylbenzilammo-
nium (MBA+), b-(methylphenethylamine) (MPEA), 1-(1-naphthyl)ethylammonium
(NEA+),37 1-(4-chlorophenyl)ethylammonium (CMBA+),2 have been used to achieve
a chiral transfer from the organic to the inorganic counterpart. Furthermore, asym-
metric heterocyclic amines as 3-ammoniopyrrolidinium (3AP),2 3-ammonioquinucli-
dine (3AQ),38 3-aminopiperidine cation (3APD),39 3-fluoropyrrolidinium (3-FP)6 have
also been synthetized together with 1,2-diaminocyclohexane (DACH),11 2-octyl-
amine (2OA),18 among a full list reported in Figure 3. Recently, the protonated state
of a-alanine encapsulated in a lead-based perovskite coordinating bromide or
iodide anions was also used as the first amino acid included as organic ligand.40
However, the stereocenter chirality is often a rigid source of asymmetry, hampering
a fast and efficient tuning of a switchable chiroptical signal.
The environment source is a flexible source of chirality transfer, despite not being
extensively exploited due to the harsh conditions of the synthesis. Chiral polymers12
or the supramolecular chirality of achiral Schiff base cations have been used to
induce chirality to form 1D helical PbI3 wires.41 Minghua Liu and coworkers have
recently reported supramolecular chiral templates inducing helical chirality in
CsPbBr3 nanocrystals.42 Furthermore, chiral features were observed in a CdCl4
perovskite encapsulating the achiral 4-phenylbutylamine (4PBA),43 mainly due to
molecular rotations of the organic chain.43
Chem 8, 1–23, May 12, 2022 5

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Figure 3. Schematic representation of stereocenter and axial chirality

Left side: stereocenter chirality of the chiral ligands inserted in hybrid organic-inorganic perovskites. Right side: axial chirality of switchable chiral
ligands.
Generating chirality through rotations leading to axial chirality, as also recently sug-
gested in the study conducted by Wei and Ning,44 can be an interesting source of
chirality transfer; however, until now it is mostly unexplored. It arises from the
absence of a coplanar arrangement of four groups of atoms on a chiral axis, giving
rise to twisted molecular planes. The restricted rotation around a single bond orig-
inates two enantiomers with positive or negative twists. Classic examples are the
ortho-substituted biphenyls as well chiral binols (Figure 3). Axial chirality is a flexible
source to achieve a chiral transfer since it can be reversible under chemical or photo-
physical stimuli. For instance, CPL irradiation can induce a rotation of the chiral
ligand, modulating or reverting its chirality. We foresee huge research in this area
for providing answers to how switchable chiral ligands can transfer their chiral bias
on the perovskite structure.
STRUCTURE-PROPERTY RELATIONSHIPS IN CHIRAL HYBRID

ORGANIC-INORGANIC PEROVSKITES
The structures of several chiral perovskites have been solved through X-ray diffrac-
tion in the recent years.2 The selection of the structures deposited in the Cam-
bridge Structural Database and that exhibited CD and/or circularly polarized lumi-
nescence properties are reported in Table 1, and a representative collection of
these structures is illustrated in Figure 4. Their main CD signals, as a function of
the wavelength, are graphically shown in Figure 5. Six main clusters of excitonic
couplings can be noticed in the region 300–500 nm, followed by a set of a few
monosignate signals. The first cluster of signals falls in the nm range [310:320]
with CD intensities ranging from 2 to 5 mdeg. The second one is between
320 and 350 nm with positive CD intensities from +5 to +17 mdeg, the third
one lays between 356 and 430 nm with negative intensities from 14 to 1
mdeg. The red-shifted CD signals are much more indicative of a chiral transfer
from the chiral ligand to the perovskite polyhedra owing to the separation from
the absorption region of the chiral ligands.45 These include the positive signals
in the region 450–470 nm with CD intensities ranging from +3 to +5 mdeg, the
negative signal at 470 nm with an intensity of 10 mdeg, and the positive one
at 515 nm with 15 mdeg. The chiral perovskite structures showing only monosig-
nate bands are the (R-MBA+)PbBr3 and (R-MBA+)PbI3 structures described in the
study conducted by Dang et al.,46 with opposite signals. Although most of those
structures incorporates the R-methylbenzylammonium ligand that may affect the
6 Chem 8, 1–23, May 12, 2022

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Table 1. The chiral hybrid organic-inorganic perovskite deposited structures containing chiral aromatic amines with their experimental chiroptical
information.
Space
Formula Group Stoichiometry CCDC Number CD (nm) CPL(nm) PL(nm) Ref.
(R-MPEA)1.5Pb P1 A3B2X7 Structures available on the 325(+); 390 (-); N/A 528 (nanowire Yuan et al. 47
Br3.5(DMSO)0.5 journal website: https://pubs. 405 (+) crystals)
acs.org/doi/abs/10.1021/ 439
acs.nanolett.8b01616 (b phase)
(R-C8H12N)4 P21 A4B2X10 1873000 187 (-); 204 (-); N/A N/A Moon et al. 48
Bi2Br10 225 (-); 242 (+);
272 (-), 340 (+); 360 (-)
(R-C5H14N2) P21P21P21 ABX4 1821929 235 (-); 320 (+) N/A 412; 617 Peng et al. 39
PbCl4 .H2O
(R-FP)MnBr3 C2221 ABX3 1957881 280 (-); 296 (+); 630 (+) 650 Gao et al. 6
(at 293 K); 320 (-); 340 (+);
350 (+); 355(+); 370 (-)
(R-MPEA)2CuCl4 C2 A2BX4 Structures available on the 324 (+); 372 (-); 436 (-) N/A 555; 617 Sun et al. 49
journal website: https://pubs.
acs.org/doi/abs/10.1021/
acs.chemmater.0c02729
(R-MBA+)4Cu4I4 P21P21P21 A4B4X4 2077127 215 (-); 260 (+) 630 (-) N/A Yao et al. 14
+
(R-MBA )PbI3 P21P21P21 ABX3 1877051 372 (-); 389 (-) N/A 720 Dang et al. 46
(R-MBA+)PbBr3 P21P21P21 ABX3 1877050 324 (+); 328 (+); 335 (-); 450-850 (+) 720 Dang et al. 46
350 (-); 356 (-); 365 (+)
R-(NEA+)2PbBr4 P21 ABX4 2015620 320 (-); N/A 450-800 Jana et al. 37
351-390 (+)
(R-MBA+)2SnI4 P21P21P21 A2BX4 1994337 357 (+), 402 (-), N/A N/A Lu et al. 36
443 (+), 473 (-)
(R-b-MPEA+)4AgBiI8 P21 A4BCX8 2016704 470 (-), 515 (+) N/A N/A Li et al. 45
(R-AlaH)PbBr3 C2 ABX3 2058839 N/A N/A 380-640 Sirenko et al. 40
(R-AlaH)PbI3 C2 ABX3 2058840 N/A N/A 480-640 Sirenko et al. 40
+
(R-MBA ) BiI4 P212121 ABX4 2093394 220 (-); 290 (+); N/A 720 Yao et al. 50
390 (-); 420 (+);
480 (-); 520 (+)
(R)-(BrPEA)2PbI4 P 43 21 2 A2BX4 2048253 300(-); 420 (-); N/A N/A Huang et al. 34
470(+); 500 (-)
detected trend in the CD signs, it appears from Figure 5 that the excitonic cou-
plings generated from the chiral perovskites incorporating R-chiral ligands, and
deposited so far, follow the trend negative/positive/negative in the region from
300 to 430 nm and positive/negative/positive from 450 to 515 nm.
We can analyze in detail each of the signals generated from the chiral hybrid perov-
skite structures, which are summarized in Table 1. In 2017, the chiroptical signatures
of the R- and S-methylbenzylamine incorporated in a 2D lead iodide perovskite were
reported. In particular, the perovskite film prepared in 50 wt% in dimethylformamide
exhibited a set of peaks in the range 400–500 nm, mostly negative for the R-stereo-
isomer.5 In 2018, the single crystals of a 2D lead perovskite including the chiral MPEA
with the DMSO solvent directly coordinating the Pb2+ surrounded by bromide an-
ions was crystallized. It was reported to exhibit CD signals at 325 and 405 nm.
The maximum peak of PL was detected at 528 nm upon excitation at 400 nm.
Fluorescence was reported also for the beta phase whose emission was detected
at 439 nm.47 In the same year, CD signals were reported for a bismuth-based perov-
skite incorporating R- or S-1-phenyl-ethylammonium in the UV range 180–380 nm.48
Furthermore, a lead-based perovskite including R- or S-3-aminopiperidine cation
was reported to show CD with peaks at 235 and 320 nm, together with two emission
signals, one narrow at 412 nm and a broad band approaching 617 nm.39 In 2019 and
then in 2020, two chiral perovskite structures with Mn2+ metal ions were crystallized
including the R- or S-fluoropyrrolidinium (FP).6,15 These structures were based on R-
Chem 8, 1–23, May 12, 2022 7

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Figure 4. Representative crystallized chiral perovskite structures

A set of crystallized structures of chiral hybrid organic-inorganic perovskites, including the first
crystallized structures from Billing and Lemmerer 9,10 with 2D helical perovskites including the
naphthyl-based ligand (NEA +), 37 toward non-lead-based perovskites from Gao et al., 6 Yao et al., 14
and Lu et al. 36 Lead perovskite are shown in yellow, manganese in magenta, copper in green, and
tin in gray.
and S-3-(FP)MnCl3 and R- and S-3-(FP)MnBr3. As expected, the emission of the

related single crystals was observed only with bromide counterions and not with
chloride ones, owing to the lowering of the band gap upon increasing the polariz-
ability of the halide. Upon excitation at 530 nm R- and S-3-(FP)MnBr3 exhibited a
red PL approaching 650 nm, that was ascribed to the (t2g)3(eg)2 (t2g)4(eg)1 metal
transition. The enantiomers showed CPL emission from 550 to 700 nm having the
main band at 630 nm, with a gPL factor of 6.1 3 103. The enhancement of the photo-
active properties was also recently observed in a CD increase from 10 to 20 mdeg
with a bromide substitution in the para position of the phenyl ring of MBA+ organic
spacer.51 Still in 2020, copper(II)-based hybrid perovskites of R- and S-(MPEA)2CuCl4
were reported to exhibit dichroic and luminescence signatures.49 An excitonic
coupling was detected at 324 and 372 nm, with a shoulder at 436 nm, whereas their
PL was observed at 555 and 617 nm. Again in 2020, the chiral MBA was shown to
8 Chem 8, 1–23, May 12, 2022

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Figure 5. The main CD signals relative to the crystallized structures reported in Table 1
The excitonic coupling signals are well correlated with intensity in the range [20:+20] mdeg.
Monosignate signals are also detected and appear unique in the case of the (R-MBA+ )PbI 3 structure
described in the study conducted by Dang et al. 46
induce chirality in copper(I) tetranuclear clusters, with the chemical formula R- and S-
(MBA+)4Cu4I4.14 Their single crystals exhibited an intense orange luminescence and
CPL signatures approaching 630 nm, with several signals from 200 to 300 nm. In the
same year, mirror-like CD signatures were reported for R- and S-a-methylbenzyl
ammonium (MBA+)-based lead halide perovskites.46 In particular, the chiral
(MBA+)PbI3 thin films were reported to absorb in the wavelengths of 370, 372,
and 389 nm. Changing the iodide with the bromide anion a blue shift in the CD
spectra was observed also in powders (324, 328, 335, 350, and 356 nm) and in single
crystals with an excitonic coupling at 365 nm. The single crystals exhibited the PL at
720 nm, although decreasing to 620 nm, presumably owing to an oxidation process.
Later on, and again in 2020, a recent contribution pointed out the influence of asym-
metric hydrogen bonding networks in transferring the chirality from the chiral ligands
to the metal center.37 Specifically, chiral spacer cations, R- or S-1-(1-naphthyl)ethyl-
ammonium (NEA+)-induced helical distortion, and a concurrent symmetry breaking
in a lead coordinated with bromide counterions. Each PbBr6 octahedral structure
was reported to form puckered coordination shells. The tilting of neighbor metal
sites was ascribed to cause asymmetric hydrogen bonds. The CD spectra of the
related films exhibited monosignate positive bands in the range of 351–390 nm
for the R-stereoisomer and a negative one for the S-enantiomer. PL was also
reported to occur in the range of 450–800 nm, and it was also detected for lead
bromide (380–640 nm) or iodide (480–640 nm) perovskite including the
protonated state of a-alanine.40 A tin-based perovskite incorporating R- or S-
methylbenzylammonium was also reported to show CD with main peaks at at 357,
402, 443, and 473 nm.36 CD signatures were recently observed at 515 nm for
R-b-methylphenethylammonium encapsulated in a silver-based perovskite
([R-MPEA+]4AgBiI8). Interestingly, the authors pointed out that the red shift of the
signals (515 nm) should indicate a direct chiral transfer of the organic ligand to the
perovskite, rather than a contribution due to organic cations (232 nm).45 In 2021,
Chem 8, 1–23, May 12, 2022 9

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BiI4 single crystals incorporating MBA+ cation were shown to exhibit dichroic patters
from 220 to 520 nm, with a PL at 720 nm, and, in the same year, lead-based iodide
perovskite incorporating (R)/(S)-1-(4-bromophenyl)ethylamine (BrPEA) generated
dichroic signals from 300 to 500 nm.34 Considering the chiral optical signatures
detected for all these structures, it is now a challenge to elucidate the relationships
between the chiral perovskite layers and the related excitonic couplings as well as
the circularly polarized signals. It is noteworthy also to understand how those signals
can be affected by non-covalent interactions and how the chiral ligand transfers the
chiral bias in the achiral perovskite scaffold.
CHIRAL AMPLIFICATION MECHANISMS: SUPRAMOLECULAR

CHIRALITY IN THE SOLID STATE
How the chirality of the ligand affects the perovskite polyhedra, which in turn affects
the features of the chiral space group, is a subtle issue. Recent predictions based on
3D R-, S- and (R/S)-CHFClNH3PbI3 perovskites19 disclosed the orientations of the
electric dipole moments of the chiral cations, which as expected were predicted
opposite for the two enantiomers and antiparallel (but not random) in the racemic
case with a total zero polarization. The two predicted electrical dipole moment ori-
entations are consistent with the P2 chiral space group, in the presence of the chiral
enantiomer, and with the P1 centrosymmetric space group in the presence of a
racemic mixture. This report highlighted the role of the chiral ligand in affecting
the overall chiral properties of the layered scaffold. Electrostatic interactions,
together with non-covalent interactions, maintain the chiral supramolecular scaffold
of hybrid perovskites. In this regard, p-conjugated weak interactions occurring in the
naphthalene skeleton in NEA+ incorporated in a 1D lead iodide perovskite were re-
ported to affect the helicity of (PbI6)4 octahedral chains, together with the ammo-
nium cation in proximity with the iodide anion, to a larger extent with respect to the
2D-layered counterpart. These weak interactions were assumed to be responsible of
the intense gCD value of 0.04 in the 1D scaffold. Moreover, it has been recently
shown that the polarization efficiency or dissymmetry luminescence factor in
(R-MBA)2PbI4 and (S-MBA)2PbI4 microplates decreases upon increasing the temper-
ature, mostly vanishing at room temperature,17 suggesting that the chirality transfer
from the chiral ligands to the perovskite polyhedra diminishes when temperature in-
creases. Lattice distortions induced by the chiral molecules is among the most com-
mon explanations, together with enhanced electron-phonon interactions or temper-
ature-dependent spin flipping.17 However, the exact mechanism of the chiral
transfer from the single chiral molecule to the whole crystal lattice is to date not
clear. In this regard, general mechanisms of chiral amplification have been proposed
over the years for soft assemblies. One of the most popular is the ‘‘sergeants and sol-
diers’’ principle, first proposed by Green and coworkers.52 This effect was observed
during a copolymerization of an achiral isocyanate. When adding a small amount of
optically active isocyanate (less than 1 mol %), the handed helical polyisocyanate was
produced. The principle thus postulates that the chirality of the chiral centers con-
trols the supramolecular chirality of the achiral units. A second phenomenon, usually
called ‘‘majority rule,’’ relies on control of the chiral amplification through a small
enantiomeric excess in a mixture of R- and S-enantiomers.53,54 Within the majority
rule phenomenon, the chiral information is significantly amplified through a
cooperative manner, resulting in a high optical activity.53,54 Translating this chiral
amplification mechanism to chiral hybrid perovskites, the chiral ligands, owing to
non-covalent interactions between stacked ligands and electrostatic interactions
with the perovskite polyhedra, can amplify the chirality through a chiral organization.
Indeed, differently from soft organic materials, in chiral hybrid perovskites the
10 Chem 8, 1–23, May 12, 2022

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chirality of the ligand induces subtle specific distortions and salt-bridge interactions
at the level of the inorganic layer. To date, it is still not clear why the CD signal re-
ported for (R-NEA+)2PbI4 in the study conducted by Ishii and Miyasaka55 is substan-
tially the opposite signal generated from (R-NEA+)2PbBr4 reported in the study con-
ducted by Jana et al.37 A similar sign inversion was also reported for (R-MBA+)PbBr3
and (R-MBA+)PbI346 with the main bands reverting from a positive sign in the bro-
mide perovskite and negative sign in the iodide perovskite.
To rationalize the supramolecular chiral amplification in chiral perovskites, the com-

bination of experiments and simulations would bring enormous advances in this
field. The development and implementation of radically new computational tech-
niques can offer a groundbreaking opportunity for a tailored chiral material design.
CHALLENGES AND OPPORTUNITIES THROUGH SIMULATION

FRAMEWORKS TUNABLE FOR CHIRAL PEROVSKITES
Ab initio methods
Most of the simulation efforts reported until now are mainly concentrated on achiral
hybrid perovskites, where spearheaded contributions aimed at predicting their elec-
tronic structure properties and optical features,56 together with their stability and
carrier mobility.57 The first contribution on chiral hybrid perovskite simulations is
related to the predictions of 3D chiral R-CHFClNH3PbI3 and S-CHFClNH3PbI3,
together with the racemic (RS)-CHFClNH3PbI3.19 The authors proposed the substi-
tution with a fluorine or a chlorine, respectively, with Van der walls radii of 147
and 175 pm, since only a small size of the chiral cation is allowed inside the cuboc-
tahedral cavity of the 3D perovskite. Intriguingly, the size of the cations was pre-
dicted to affect the Pb–I bond length, increasing to roughly 0.203 Å in the presence
of R-CHFClNH3PbI3 with respect to the achiral CH3NH3+. The rotations of the chiral
ligands slightly distort the perovskite polyhedra. The three structures were opti-
mized at the Perdew-Burke-Ernzerhof (PBE) level58 with the Grimme’s D2 dispersion
correction method.19 Interestingly, upon removing the chiral ligand, the chiral
arrangement of the perovskites was observed to be maintained, indicating a chiral
transfer from the ligand to the metal coordination site. Furthermore, negative forma-
tion energies were predicted for the analyzed 3D chiral perovskites that, together
with ab initio molecular dynamics and phonon spectra calculations, indicated both
thermodynamics and kinetics stability at 300 K. The band gap was predicted to be
1.24 eV for the achiral and 1.51 eV for the chiral enantiomers within the hybrid
Heyd-Scuseria-Ernzerhof 2006 (HSE06) functional.59 Spin splitting calculations
have been recently carried out at the PBE level, including dispersions with the
vdWs-optB86b functional60 and the DFT-D2 method, to study the effect of the
halide substitution at the chiral carbon of MBA+ in Pb–I-based chiral HOIPs, where
an enhanced energy gap was predicted in the order Br > Cl > F.61 It is also worth
noting that the electrostatic potential surface of the chiral molecules was predicted
to significantly affect the arrangement of the inorganic layers.61
A general accepted simulation protocol derived from previous ab initio studies on

achiral perovskites is to choose the PBE58 functional with the D2 dispersion correc-
tion for structural calculations and the HSE06 for the energetics. The PBE58 exchange
correlation functional and its revised version for densely packed solids (PBEsol)62
emerged over the years as the density functionals that more correctly describe metal
halide perovskites’ electronic structures.63–65 The hybrid revised version of the PBE
density functional has been generally used for the band-gap predictions or photo-
physical-chemical properties.65 Furthermore, in the case of layered structures, it
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has been shown that the use of dispersion-corrected functionals, for example with
the Grimme’s D2 or D3 correction method, is necessary to achieve accurate struc-
tural predictions.63 However, all these studies pointed out how standard DFT func-
tionals (GGA and LDA, which stand for generalized gradient approximation and
local density approximation, respectively) usually exhibit a systematic underestima-
tion of the electronic band gaps for the metal halide perovskite system, as a conse-
quence of the poor treatment of the exchange correlation functional. In this regard,
the use of hybrid non-local functionals is one of the mainly adopted approaches.
Several works have shown that the HSE06 hybrid functional,59 accounting for non-
local exchange interactions by including a percentage of Hartree-Fock exchange,
describes the band gap of metal halide perovskites with a good accuracy, by
requiring a slightly higher computational cost compared with standard DFT func-
tionals.64,65 Moreover, the use of higher level of theory, such as the many-body
GW methods often used to correct errors in the one-electron Kohn-Sham eigen-
values within a many-body quasiparticle framework, allows getting a very accurate
evaluation of the band gap and optical absorption, though at higher computational
cost.66 Indeed, the presence of heavy atoms requires the treatment of relativistic ef-
fects including the SOC effects. Those nearly scale with the square of the atomic
masses, making these contributions progressively important moving down the peri-
odic table.67 Those are both accurate methods but require a massive computational
workload. An interesting possibility is the pseudo self-interaction correction (VPSIC)
approach, which was recently used for stannates and shown to be of an accuracy
similar to hybrid HSE hybrid functional, albeit substantially less computationally
demanding.68
Force-field developments
Ab initio simulations have nowadays reached high quantum chemical accuracy for
rigid molecular blocks of medium size. However, when searching for different molec-
ular geometries that can be accessible with thermal stimuli, slow molecular rear-
rangements usually require a high and often unaffordable computational demand
to reach micro or millisecond timescale. Consequently, molecular dynamics simula-
tions based on classical force fields are continuously receiving an increasing interest.
The reduced computational cost of classical models makes it affordable for the simu-
lation of large systems (up to millions of atoms for nanoseconds) that are typically
out-of-reach of ab initio quantum chemical calculations. Therefore, force-field-
based simulations are very useful for the study of hybrid perovskites.
The first example of classical force-field for hybrid perovskites is the MYP model
developed by Mattoni et al. to study the picosecond dynamics of organic cations
in methylammonium lead iodide.69 MYP model combines ionic Buckingham-
Coulomb interactions for metal halides with bonding-electrostatic-dispersive forces
for organic molecules. The model reproduces the main structural properties, phase
transitions, and phonons of bulk iodides70 and bromides,71 but it has been also
applied to surfaces,72 interfaces with liquids,73 grain boundaries,74 ferroelastic do-
mains,75 and point-defects76,77 for a broad range of properties including thermal
conductivity, hysteresis-memory effects, ionic polarization, and degradation in hu-
mid conditions.78 Additional parametrization of the model has also been applied
to surface passivation by ligands79 and nucleation phenomena in liquid solvents.80
Notably, recent progress is represented by machine-learning (ML)-derived inter-

atomic potentials. The idea is to train neural network potential by using ab initio
datasets.81 One interesting strategy is to learn on the fly during ab initio molecular
dynamics. Such methodology provided quantitative description of the phase
12 Chem 8, 1–23, May 12, 2022

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Figure 6. Classical molecular dynamics for hybrid perovskites and chirality induction mechanisms
(A) Applications of atomistic modeling based on classical force fields to: (A) rotational dynamics of
organic cations across phase transitions in MAPI; reprinted with permission from Mattoni et al. 69
Copyright 2015, American Chemical Society.
(B) Study of point defects diffusion and trapping at grain boundaries of hybrid perovskites
explaining the observed degradation of regions exposed to light and the subsequent recovery in
dark. 74 Reprinted with permission from Phung et al. 74 Copyright 2020 Phung et al. Adv. Ener. Mater.
1903735.
(C) Study of the ultralow thermal conductivity of two-dimensional hybrid perovskites, Giri et al. 85
(D) A schematic illustration of a chirality induction mechanism triggered by light-irradiation and
thermal effects enabling molecular rotation. The asymmetry of transition states can select different
free-energy pathways, reaching thermally and light-activated chiral free-energy basins.
transitions of hybrid and inorganic crystals.82 Multiscale approaches that combine

ML interatomic potentials and Monte Carlo methods also have been proposed and
applied to perovskites alloys.83 In the perspective of chiral perovskites, model po-
tentials for two-dimensional Ruddlesden-Popper structures or other low-dimen-
sional 2D or 1D structures are of great interest. Recent computational studies
based on MYP and similar interatomic potentials have shown the transferability
of classical models to 2D systems by reproducing, at least qualitatively, the struc-
ture,84 phonons, heat capacitance, and thermal conductivity85,86 of prototypical
2D lead halides (Figures 6A–6C). The application of classical models to chiral
Chem 8, 1–23, May 12, 2022 13

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hybrid perovskites is still largely unexplored, but applications to hybrid perovskites

suggest that they can be a powerful tool for the theoretical design of chiral struc-
tures. The success of classical methods is critically related to the accuracy of the
models. It is expected that ML-derived force fields, by improving accuracy and
transferability, will push forward the importance of atomistic modeling for chiral
systems.
Enhanced sampling simulations

Long timescales of classical simulations (up to microseconds) possibly coupled to
accelerated dynamics are important to adequately sample the configurational
space. These requirements are particularly relevant for chiral systems characterized
by complex hybrid organic-inorganic, long-range ordering effects, layered struc-
tures, and long or twisted chiral molecules able to transfer chirality to the inorganic
lattice by slow reorganization mechanisms. These high conformational degrees usu-
ally spawn high energy barriers between molecular coordinates causing a timescale
drawback, which hampers exhaustive conformational sampling. To overcome this
limitation, several methods have been developed to enhance the sampling,87 with
force-field potentials derived at ab initio levels on molecular block units. Most of
them rely on adding a bias potential to the Hamiltonian of the systems for decreasing
the energy barrier, thereby reaching transition states. In the first category, the bias is
deposited along one or more reaction coordinates during the enhanced sampling
simulations, such as metadynamics-based algorithms88 and adaptive biasing force
method,89 among many others.87
This category works well if the mechanism is described through established collective
variables. By contrast, if the collective variable is not so straightforward to identify, a
second category of methods that does not require any collective variables, like the
popular replica exchange method (REM),90 is usually preferred. To predict the
chirality induction and transfer from a chiral ligand to an achiral core, temperature ef-
fects coupled with light irradiation need to be carefully considered (Figure 6D). In this
regard, a recent simulation framework91 combined the use of REM,90 parallel bias
metadynamics,92 and free-energy perturbation (FEP)93 theory to simulate the free-
energy pathways from ground to excited states,94 proposing the bias of temperature
and light irradiation. A transfer of the asymmetry from transition states can generate
amplified supramolecular chiral conformations through stepwise rotations eventually
stabilized through transition state asymmetry, a theory elegantly described by Astu-
mian in which molecular rotors can function selecting preferred paths, based on the
asymmetry of transition states.95 This intrinsic asymmetry can select different path-
ways based on the lowest energy barrier.96 Consequently, enhanced sampling
methods are very appealing to predict the chiral perovskite structures, and a combi-
nation of methods with accurate force fields tailored for hybrid perovskites can
further enhance the exploration of their asymmetry.
PERSPECTIVE ON APPLICATIONS OF CHIRAL HYBRID PEROVSKITES

We finally provide a brief outlook on applications by chiral hybrid perovskites.
Indeed, reports on chiral perovskites properties are continuously increasing, and
we expect huge developments in this field of intense research.
We anticipate two main directions of applications for chiral hybrid perovskites: (1)
chiroptics and (2) chiral spintronics. Within tridimensional chiral perovskite frame-
works ferroelectricity can be also prospected and exploited for novel bespoke
non-volatile memory devices.
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Figure 7. Chiroptical properties of a low-dimensional chiral perovskite

(A–D) CD, g CD and PL spectra of R-, S- and racemic (a-PEA)PbI 3 , with a scheme reported in (C).
Reprinted with permission of Chen et al. 4 Copyright ª 2019, Springer Nature Limited.
Chiroptical applications
Among the chiroptical applications, CPL photodetectors are among the most prom-
ising fields. Indeed, a special interest has been devoted to chiral HOIPs for CPL pho-
todetectors—an innovative concept that exploits left-handed and right-handed CPL
as two independent channels to transmit information, doubling the rate of data
transport compared with unpolarized light.
In more detail, to develop an efficient CPL photodetector at increased sensitivity,

the factor
nL nR Dad
z
ðnL + nR Þ 2 eaL d 1
=
must be optimized, where nL and nR are respectively carrier concentration generated

by left circularly polarized (LCP) and right circularly polarized (RCP) light, aL and aR
are the absorption coefficient of LCP and RCP light, Da is equal to aL aR , and d is
the thickness of the crystal.
To maximize the ratio, once should maximize the Da, index of material’s chirality,
while reducing concomitantly the active material thickness.4 For this reason, a thin
film with high chirality is preferred for device optimization. A study demonstrating
a CPL detector by using a low-dimensional perovskite has been reported in 2019,4
showing a remarkably high responsivity and long stability. They used chiral a-phen-
ylethylamine in the form of right-hand (R-a-PEA) and left-hand (S-a-PEA) enantio-
mers to synthesize chiral perovskite (see structure in Figure 7). The p bond in the
benzene ring of a-PEA facilitates columbic interaction between chiral amines and
(PbI6)4 matrix, increasing the CPL-sensitive absorption. First, they produced single
Chem 8, 1–23, May 12, 2022 15

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crystals of perovskite (R- and S-a-PEA)PbI3 by the inverse temperature crystallization

method, and then they dissolved them in DMF solution to fabricate (R- or S-a-PEA)
PbI3 films. They also prepared the racemic film (rac-a-PEA)PbI3 with a precursor
containing (R- and S-a-PEA)PbI3 with a ratio of 1:1. Both (R- or S-a-PEA)PbI3 films
exhibited strong CD signals, a phenomenon in which a material absorbs more
of one circular polarization than the other, making the transmitted light
elliptical, in contrast to the (rac-a-PEA)PbI3 counterpart, which is possible to notice
in Figure 7.
The parameters that can describe, quantitatively, the degree of chirality are the ellip-
ticity q (Equation 1), expressed in mdeg or the anisotropy factor gCD (Equation 2),
whose mathematical expression are written below:

ln10 180000
q ðmdegÞ = DA (Equation 1)
4 p
AL AR
gCD = (Equation 2)
AL + AR =2
where DA is the difference in absorption of the left-handed (AL) versus right-handed

(AR) CPL, and gCD range from 2 (absorbing only right-handed CPL) to 2 (absorbing
only left-handed CPL), with 0 indicating the absorption of both equally.
From Figures 7A and 7B it is possible to notice that for the chiral perovskites the CD
spectra showed two intense peaks at 328 and 392, related to two excitonic transi-
tions in (a-PEA)PbI397 and the anisotropy factor of CD. At 392 nm gCD is 0.02, three
times higher than that of (a-PEA)2PbI4 perovskite. In order to further verify this point,
(a-PEA)PbI3 films were assembled into photodetector devices (Figure 7C). Figure 7D
showed the responsivity and photoconductor gain of (R- and S-a-PEA)PbI3 photode-
tectors under the CPL with the wavelengths of 365, 395, 430, and 530 nm. It is sig-
nificant to notice that under an illumination with a wavelength of 395 nm, maximum
responsivity and photoconductor gain are achieved, 0.12 AW1 and 39.0%, respec-
tively. In addition, the differences in responsivity between LCP and RCP are promi-
nent at the wavelength of 395 nm, in contrast with the others, which is consistent with
the CD and gCD spectra. With light intensity dependent measurements, it has been
shown that the responsivity can reach 797 mAW1 (with an irradiance of 252 mW
cm2), 200 times higher than in metamaterial-based CPL detectors. However, at
this stage, the performance of CPL photodetectors is still far from that required
for practical applications. In order to improve the performances of CPL-insensitive
photodetectors (such as CH3NH3PbX3-based ones, which show responsivities of
the order of tens AW1),98 further optimization is required. An efficient method is
to increase the anisotropy factor of chiral perovskite materials, which can be
achieved by improving film quality or by integrating chiral materials in heterostruc-
ture with different architectures. Improving those aspects can provide guidance for
further optoelectronic device applications.
In this regard, 2D perovskites based on R- and S-(MBA+)2PbI4 crystals have been

reported to show a CPL average degree of 9.6% and 10.1%, respectively, with
a maximum degree for the S-enantiomer of 17.6%.17 More recently, quasi-2D chi-
ral-perovskite single crystals based on (R-MPEA)2MAPb2I7 and adopting the Rud-
dlesden-Popper phase have shown notable performances of RCPL over LCPL, with
an external quantum efficiency (EQE) of 882% under RCP illumination, higher than
the metamaterial-based CPL detectors with a gIph anisotropic photocurrent factor
of 0.2 at 10 V bias voltage, comparable to state-of-the-art CPL photodetectors.28
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Circularly photogalvanic effect was observed in single crystals of a lead iodide

perovskite containing (R)/(S)-1-(4-bromophenyl)ethylamine, with a spin-polarized
current generated without any bias voltage with opposite signs of the two enantio-
mers.34 CISS was also recently introduced to produce a spin-LED operating without
an external magnetic field or ferromagnets, which achieved 2.6% of CPL at room
temperature in chiral 2D-layered lead-based hybrid perovskites.8
Chiral spintronics
A twisted asymmetric molecule can have a right-handed or left-handed chirality de-
pending on the sign of the dihedral angles defining the molecular scaffold.99 When a
spin crosses a chiral structure with a broken reflection or inversion symmetry, it can
be polarized generating a spin current through spin-orbit interaction.100 Indeed, the
projection of the spin under the direction of motion can be parallel or antiparallel
giving rise to a right-handed or left-handed helicity. When the electron spin crosses
a chiral molecule, the molecular handedness affects the electron tunneling probabil-
ity, which is dependent on its spin direction. This is the well-known CISS.3 For
instance, spin transport occurring via the CISS mechanism was recently observed
in 2D HOIPs through the introduction of chiral organic spacers.101 A vertical charge
transfer was observed through multiple vertical helical potentials in the thin 2D
hybrid perovskite film and without oriented monolayers, achieving a spin-polariza-
tion transport of up to 86% that has improved to 94% with tin-based 2D HOIPs still
including MBA+,36 presumably due to a strong distortion of the tin perovskite octa-
hedra resulting from hydrogen bonds between the ammonium groups and iodide
anions. The latter is the largest distorted single crystal structure reported so far
among the reported layered tin iodide perovskites. Furthermore, the spatial symme-
try breaking through the spin-orbit interaction removes the 2-fold spin degeneracy,
an effect observed by Dresselhaus and Rashba in non-centrosymmetric zinc-
blende102 and wurtzite structures.103 The Rashba effect is associated with a spin
splitting in which the electron energy bands En(k) is linear in each wave vector k in
the Brillouin zone and shows a helical spin texture. The Dresselhaus effect, on the
other hand, is related to a spin splitting that is cubic in k, and the spin texture is
non-helical.104 Recently, the Rashba-Dresselhaus (RD) spin splitting has been pre-
dicted in 2D chiral HOIPs based on 1-(1-naphthyl)ethylammonium lead bromide in
the DFT framework within HSE06-SOC (Figure 8). The authors estimated the ERD en-
ergy difference of 55 meV, orders of magnitude higher than those found in InAlAs/
InGaAs structures37 but similar to 2D phenethylammonium lead iodide HOIP. Mitzi
and colleagues postulated that temperature possibly coupled with photoexcited
coherent phonon modes can induce the band splitting in phenethylammonium
lead iodide.37 The spin splitting was predicted to increase with local inorganic layer
distortions induced from the organic cations105 as well as with the halogen substitu-
tion (Br > Cl > F) within the MBA+ chiral organic spacer.61 The halogen substitution
can lower the crystal symmetry of HOIPs even when involving achiral organic
spacers.106
These results are encouraging for moving toward this research area considering that
chiral perovskites can be inherently ferromagnetic as well as CPL emitters, enabling
the spin polarization without the need for an external magnetic field or circularly
polarized excitation.
OUTLOOK ON APPLICATIONS AND FUTURE PERSPECTIVES

Spintronic devices (as discussed above in the context of chirality) are designed to
take advantage of the interaction between the external magnetic field and the
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Figure 8. Schematic representation of chiral and racemic hybrid perovskites and their relative
electronic band structures
(A) Spin degeneracy of the electronic bands, relative to the racemic HOIP on bottom.
(B and C) The spin splitting sub-bands with down spin in red, upper spin in blue with the energy
difference DE at the typical momentum k 0 , relative to the chiral R,S HOIP on bottom.
Figure adapted from Jana et al. 37 Copyright ª 2020, Springer Nature Limited.
carriers. From the perspective of storage and information technology, spintronics

constitutes a combination of electronics and magnetism, entrusting binary coding
to the spin of the carriers (or, in general, angular momentum) that represents an
additional degree of freedom to carry information.
Conversely, electronic devices are based on the electronic charge of carriers (i.e.,
charge-based) so that the only way to modulate carriers is the electric fields applied
to electrodes. A major drawback of charge-based devices is the Joule heating,
leakage currents, and other issues related to energy consumption or the need for
continuous energy supply.
Chiral materials are not only attractive for spintronics but also for charge-based elec-
tronics, particularly if it is possible to have ferroelectric phases, obtained through the
design of suitable chiral molecules and inorganic lattices. Ferroelectric chiral perov-
skites are in principle possible as the crystallographic space groups of chiral mate-
rials are compatible with possible ferroelectric distortions.
If ferroelectricity can be achieved in chiral materials, interesting applications (based

on ferroelectric chiral materials with in-plane polarization P) are expected: non-
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volatile-memory devices, electrocaloric devices, ferroelectric random-access mem-

ories, and dynamic random-access memory capacitors. 3D chiral materials are highly
desirable for nanoelectronics and charge-based devices, since they have smaller
exciton-binding energies and longer carrier-diffusion lengths, which should prove
advantageous in chiroptoelectronics.
Although great progress has been made in order to explore ferroelectric properties
of 1D and 2D organic-inorganic perovskites for next-generation optoelectronic de-
vices, 3D perovskites structures remain challenging in metal halides. This is ulti-
mately related to structural constraints (i.e., tolerance factor) limiting the 3D
organic-inorganic framework to contain only small size cations (such as [CH3NH3]+
and [NH2CHNH2]+). Molecules can bring permanent dipoles (e.g., methylammo-
nium) favoring ferroelectric configurations at low temperatures (e.g., in the ortho-
rhombic phase); however, the occurrence of thermal orientational disorder (almost
isoenergetic domains with different polarization75 or fast molecular rotations in
the tetragonal and cubic phases69) can suppress a stable ferroelectric response.
For this reason, the design of new 3D organic-inorganic perovskites in which stron-
ger hybrid interactions can lead to a robust macroscopic ferroelectric distortion is
still a challenging issue107 and requires the design of novel systems.
Among the potential candidates for the development of quantum bits, spin is indeed
one of the best choices. In the field of spintronics and quantum communication, we
expect great potential from the development of chiral materials.
Very appealing are the possibilities related to ‘‘spin manipulation and spin trans-
port.’’ Spin devices require imbalanced population of different spin species of cur-
rent. In achiral materials, circularly polarized excitations or external magnetic fields
are needed. Chiral perovskites could enable optical spin manipulation due to their
asymmetric circular polarization absorption and emission rates. This could lead to
controlling the relative abundance of carriers with different spin, even under contin-
uous, unpolarized excitation and could be utilized to create a spin current either in
the perovskite itself or by spin injection into a ferromagnetic material.
Spintronic circuits
By achieving good control of materials’ chirality, for example, by varying the organic
cations within hybrid crystalline layers, it is in principle possible to grow heterostruc-
tures with different handedness of chirality. The synthesis of sharp interfaces could
drive to the realization of some sort of spin diodes and chiral-based spin transistors,
eventually realizing the elements for a chiral-based spintronic circuitry. Other appli-
cations could be ‘‘spintronic photodiodes and LEDs,’’ in which the detection of light
results in a spin current, and the emission of light depends on a spin current. All these
devices would work under a zero magnetic field.2
Another interesting perspective could derive from the possibility to directly switch
chirality (e.g., by ligand rotations) by the application of suitable stimuli (i.e., stress,
temperature, and electric or magnetic field). This could enable the applications of
chiral perovskites for storing information by using chirality. Indeed, various types
of chiral hybrid perovskites have been designed for next-generation chiroptical or
chiral spintronics materials, with different architectures of the inorganic and organic
counterparts. Indeed, challenges and drawbacks still exist (i.e., the actual perfor-
mance of CPL photodetectors are still far from being ready for practical applica-
tions); however, the huge efforts that have been made are encouraging for moving
toward the implementation of this kind of chiral materials for widespread
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Review
applications. The mechanism of molecular rotations and its induction in chiral hybrid
perovskites are to date unexplored and neither exploited in predictive modeling nor
simulations. Indeed, restrictions of molecular motions in excited states are known to
enhance photoemissions,108 including the CPL ones.109 However, no available
computational datasets are present for chiral perovskites, and therefore chiral multi-
scale simulations on these materials can become the building blocks for learning-
based algorithms to guide the chiral experimental design. This review has investi-
gated key points that we want to share widely to unlock new unexplored chiral
design concepts on chiral hybrid perovskites. We believe that molecular rotations
leading to axial chirality for a flexible asymmetry and distorted excited states that ac-
count for an increase in CPL emissions can be exploited also in chiral hybrid perov-
skites, with the advantage of a switchable and controllable chirality.
ACKNOWLEDGMENTS
PRIN2017 2017WBZFHL_003 (AP) is acknowledged for financial resources. A.M. ac-
knowledges Italian Ministry MUR for project PON04a2 00490 M2M Netergit and Ital-
ian National Research Council CNR for bilateral project CNR-RFBR
B55F21000620005. The authors acknowledge the ‘‘HY-NANO’’ project that has
received funding from the European Research Council (ERC) Starting Grant 2018 un-
der the European Union’s Horizon 2020 research and innovation programme (grant
agreement no. 802862) and from the project FARE Ricerca in Italia EXPRESS (no.
R18ENKMTA3).
AUTHOR CONTRIBUTIONS
A.P., A.M., and G.G. proposed the topic of the review. G.P., M.F., and G.S. collected
literature data. M.F. and G.P. prepared the draft manuscript. A.P., A.M., and G.G.
discussed and revised the manuscript.
DECLARATION OF INTERESTS
The authors declare no competing interests.
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Rationalizing the design and implementation of chiral hybrid perovskites

Article in Chem · February 2022

Adriana Pietropaolo Alessandro Mattoni

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Giovanni Pica Mariagrazia Fortino

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SUMMARY The bigger picture

Chem 8, 1–23, May 12, 2022 ª 2022 Elsevier Inc. 1

BACKGROUND ON HYBRID ORGANIC-INORGANIC PEROVSKITES

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Figure 1. Examples of chiral halide perovskites

structure without distortions. Indeed, the tolerance factor is an empirical formula

Apart from the 3D structures of perovskites, the 2D perovskites are generally

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Figure 2. Schematic representation of 2D perovskite structures and their applications

long-chain organic ligands whose length, together with reaction temperature,

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CHIRAL HYBRID ORGANIC-INORGANIC PEROVSKITES: DESIGN

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Figure 3. Schematic representation of stereocenter and axial chirality

STRUCTURE-PROPERTY RELATIONSHIPS IN CHIRAL HYBRID

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Figure 4. Representative crystallized chiral perovskite structures

and S-3-(FP)MnCl3 and R- and S-3-(FP)MnBr3. As expected, the emission of the

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CHIRAL AMPLIFICATION MECHANISMS: SUPRAMOLECULAR

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To rationalize the supramolecular chiral amplification in chiral perovskites, the com-

CHALLENGES AND OPPORTUNITIES THROUGH SIMULATION

A general accepted simulation protocol derived from previous ab initio studies on

Chem 8, 1–23, May 12, 2022 11

Notably, recent progress is represented by machine-learning (ML)-derived inter-

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transitions of hybrid and inorganic crystals.82 Multiscale approaches that combine

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hybrid perovskites is still largely unexplored, but applications to hybrid perovskites

Enhanced sampling simulations

PERSPECTIVE ON APPLICATIONS OF CHIRAL HYBRID PEROVSKITES

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Figure 7. Chiroptical properties of a low-dimensional chiral perovskite

In more detail, to develop an efficient CPL photodetector at increased sensitivity,

must be optimized, where nL and nR are respectively carrier concentration generated

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crystals of perovskite (R- and S-a-PEA)PbI3 by the inverse temperature crystallization

where DA is the difference in absorption of the left-handed (AL) versus right-handed

In this regard, 2D perovskites based on R- and S-(MBA+)2PbI4 crystals have been

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Circularly photogalvanic effect was observed in single crystals of a lead iodide

OUTLOOK ON APPLICATIONS AND FUTURE PERSPECTIVES

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carriers. From the perspective of storage and information technology, spintronics

If ferroelectricity can be achieved in chiral materials, interesting applications (based

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volatile-memory devices, electrocaloric devices, ferroelectric random-access mem-

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