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Controlling Nonlinear Optical Switch of Diarylethene by
Changing Sizes of Fullerene: A Theoretical Study
Xiantao Xiong+,[a] Fengyi Zhang+,*[a] Yongjun Zhang,[a] Xiaoyu Zhao,[a] Hongliang Xu,[b]
Kun Zhang,[a] and Yaxin Wang*[a]
Fullerene is a material with good electrical conductivity and
thermal stability, and its size is an important factor to influence
its photoelectric property. In this work, effect of fullerene size
(C20, C60, and C70) on nonlinear optical (NLO) switchable
molecule diarylethene (DAE) was explored. In the aspect of
molecular NLO properties, it could be found that the static first
hyperpolarizability βtot of Cx-O (x=20, 60, 70) was larger than
that of Cx-C (x=20, 60, 70), and the βtot difference between
open-ring and closed-ring structure increased from 19 to
1431 au with the size of fullerene increased. Especially for C70-
DAE, its largest contrast of βtot values between open-ring and
closed-ring structure suggested its superiority among three
groups of NLO switchable complexes. The result could attribute
to C70-O exhibits a strong dipole characteristic, whereas C70-C
displays a weak dipole characteristic. By analyzing dynamic first
hyperpolarizability, it could be found large NLO response
mainly depended on molecular dipole characteristics. As a
result, for C70-DAE, βHRS of open-ring structure was still larger
than that of closed-ring structure. However, the dynamic first
hyperpolarizability βHRS of open-ring structure was smaller than
that of closed-ring structure in both C20-DAE and C60-DAE. The
switching efficiency was reversed.
Introduction
Nonlinear optics (NLO) originates from the nonlinear interaction
between the medium and incident light. With the successful
development of the first ruby laser, some NLO phenomena such
as Kerr effect, two-photon absorption and harmonic generation
were observed and applied in optical data processing, trans-
mission, storage, and so on.[1] Among these, the investigation of
switchable NLO properties has emerged as a promising avenue
for exploring NLO response and is currently garnering increas-
ing attention.[2] There have been many NLO switches controlled
by different stimuli such as redox,[3] temperature,[4] pH[5] and so
on. Among them, photochromic molecules with light-induced
reversible change of conformation attracted our attention.[6]
Due to changes in molecular structure and electron redistrib-
ution, different states are often accompanied by different
optical and magnetic properties,[7] and applied in fields of
biology, medicine, and materials science.[8] In the field of NLO,
reversible conformational changes are accompanied by a
significant on-off NLO response, making them highly promising
for applications in emerging optoelectronic and photonic
technologies. Thus, many photochromic species such as
azobenzene, spiropyran, and diarylethene are ideal materials for
designing photoswitchable secondary NLO materials.[9]
Diarylethene (DAE) is one of the typical photochromic
molecular switches and has received extensive attention
recently due to its fatigue resistance, photostability, and fast
switching properties.[10] DAE was firstly reported by Irie and
Mohri,[11] and its open-/closed-ring isomerization was found at
the same time. The isomerization process of DAE was followed
by significant change of conjugation, dipole moment, color,
glass transition temperature, metal-vapor deposition property
and many electrical properties.[6,12] Thus it has been extensively
investigated in aspects of tunable molecular conduction
junctions,[13] optical functional materials for photonic
upconversion,[14] molecular device[15] and so on. In the work of
Zhang et al. (2019), they introduce a building-block design
strategy to achieve DAE all-visible-light photochromism with
the triplet-sensitization mechanism.[16] In NLO, by modifying the
metal complex decorated with DAE or designing a push-pull
structure, the NLO can be further controlled.[17] Therefore,
studying the modification of DAE for regulating NLO holds
great significance.
Fullerenes are a class of carbon cluster as electron acceptors
with high π-electron conjugation. Classical fullerenes such as C60
are composed of five-membered and six-membered rings. As a
functional group capable of modifying other structures, full-
erenes possess various advantages, such as stability, excellent
electron transport properties, and adjustable optical
properties.[18] These advantages offer a wide array of possibil-
ities for the functionalization and performance enhancement of
materials. For instance, Liu et al. reviewed the development of
fullerene derivatives in solar cells, organic thermoelectrics and
other fields.[19] Tuktarov et al. (2017)[20] conducted a comprehen-
[a] X. Xiong,+F. Zhang,+Y. Zhang, X. Zhao, K. Zhang, Y. Wang
School of Material and Environmental Engineering,
Hangzhou Dianzi University,
Hangzhou, 310018, P. R. China
E-mail: yaxinwang@hdu.edu.cn
zhangfy.hdu@hdu.edu.cn
[b] H. Xu
Institute of Functional Material Chemistry, National & Local United
Engineering Laboratory for Power Batteries, Department of Chemistry,
Northeast Normal University,
Changchun, 130024, P. R. China
[+]These authors contributed equally to this work.
Supporting information for this article is available on the WWW under
https://doi.org/10.1002/slct.202304717
Wiley VCH Montag, 08.04.2024
2414 / 347902 [S. 212/219] 1
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