Coordination Chemistry Reviews 414 (2020) 213300

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Coordination Chemistry Reviews

journal homepage: www.elsevier.com/locate/ccr

Review

Recent progress on supramolecular assembly of organoplatinum(II)

complexes into long-range ordered nanostructures
Yifei Han, Zongchun Gao, Cong Wang, Ruolei Zhong, Feng Wang ⇑
CAS Key Laboratory of Soft Matter Chemistry, Department of Polymer Science and Engineering, University of Science and Technology of China, Hefei, Anhui 230026, PR China

a r t i c l e i n f o a b s t r a c t

Article history: Organoplatinum(II) complexes have received enormous attention because of their intriguing photo-
Received 2 December 2019 physical and chemotherapeutic behaviors. They are also regarded as excellent building blocks for
Received in revised form 2 March 2020 supramolecular assembly due to the square planar geometry and coordination unsaturation characters,
Accepted 14 March 2020
which facilitate to incorporate p–p stacking, Pt(II)–Pt(II) metal–metal and other non-covalent interac-
Available online 2 April 2020
tions together. In this review, we have summarized the state-of-art progress of organoplatinum(II)-
based long-range ordered nanostructures, as catalogued by the diverse assembling modes. In addition,
Keywords:
potential applications of organoplatinum(II)-based supramolecular nanostructures in optoelectronics,
Supramolecular assembly
Organoplatinum(II) complexes
sensing, and biomedical fields are briefly introduced.
Metal–metal interactions Ó 2020 Elsevier B.V. All rights reserved.
Pathway complexity
Supramolecular materials

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2. Construction of organoplatinum(II)-based supramolecular nanostructures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2.1. Primary self-assembly of monodentate Pt(II) complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2.2. Primary self-assembly of multidentate Pt(II) complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
2.3. Hierarchical assembly of Pt(II) complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
2.4. Assembly of Pt(II) complexes into diverse morphologies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
2.5. Pathway complexity in assembling Pt(II) complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
2.6. Multi-component co-assembly of Pt(II) complexes. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
2.7. Hybrid co-assembly with the presence of Pt(II) complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
3. Functionality of organoplatinum(II)-based supramolecular nanostructures. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
3.1. Sensing materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
3.2. Emitting materials. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
3.3. Semi-conductive materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
3.4. Biomedical materials. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
3.5. Other potential applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
4. Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
Conflict of interest . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
Appendix A. Supplementary data . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18

⇑ Corresponding author.
E-mail address: drfwang@ustc.edu.cn (F. Wang).

https://doi.org/10.1016/j.ccr.2020.213300
0010-8545/Ó 2020 Elsevier B.V. All rights reserved.
2 Y. Han et al. / Coordination Chemistry Reviews 414 (2020) 213300
1. Introduction
Platinum(II) complexes represent an important type of transi-
tion metal complexes with d8 electron configuration and square
planar geometry. When organic ligands are bound to the metal
center, a variety of organoplatinum(II) complexes generate with
mono- and multi-dentate character [1–3]. Spin–orbit coupling
between the metal and ligand units renders fruitful photo-
physics to the resulting organoplatinum(II) complexes, including
ligand-centered (LC), metal-to-ligand charge transfer (MLCT), and
ligand-to-ligand charge transfer (LLCT) electronic transitions, etc.
[4,5]. As a consequence, the absorption/emission wavelength, the
emission intensity/lifetime, and the Stokes shifts can be elabo-
rately modulated, which are promising for organic light-emitting
diodes (OLEDs), sensing, and bio-imaging applications [6,7].
Besides, the organoplatinum(II) complexes have shown bright pro-
spect in chemotherapeutic fields [8], attributing to the clinical suc-
cess of cisplatin [Pt(II)Cl2(NH3)2] for the anti-cancer applications.
Bottom-up supramolecular assembly exists ubiquitously in nat-
ural biological systems such as DNA and proteins. In view of its low
cost and convenient fabrication characters, supramolecular assem-
bly has become an effective technique toward long-range ordered
nanostructures with the emergent functions. Up to now, various
artificial supramolecular assemblies have been established on the
basis of small molecules, polymers, and inorganic nanoparticles
[9–11]. Organoplatinum(II) complexes also represent ideal
supramolecular building blocks due to the square planar geometry
and coordination unsaturation characters, which display strong
tendency to stack with each other. The resulting long-range
ordered nanostructures are endowed with some fascinating prop-
erties. First, supramolecular assembly generates the rigidifying
effect for organoplatinum(II) complexes. The declince of non-
radiation decay rate, together with the shielding of chormophore
from the environment, could potentially give rise to the emission
enhancement property [12]. Second, supramolecular assembly is
often accompanied by Pt(II)–Pt(II) orbital overlapping of the neigh-
bouring organoplatinum(II) complexes. Accordingly, 5d2z orbitals
are re-organized into low-lying dr and high-lying dr* orbital for
the Pt atoms, leading to the appearance of metal–metal-to-ligand
charge transfer (MMLCT) transition at low-energy visible/NIR
Scheme 1. Typical organoplatinum(II)-based chemical structures for supramolecular assembly.
region [13–15]. The emergent spectral transition at the biologically
interesting window would benefit for the biomedical applications
of organoplatinum(II) complexes. Third, the modular incorporation
of various functional groups imparts multifunctionlity and adapt-
ability to the resulting supramolecular nanostructures [16]. In this
context, supramolecular assembly of organoplatinum(II) com-
plexes has achieved considerable progress over the last two dec-
ades [17–22].
Up to now, both monodentate and multidentate (including bi-,
tri- and tetra-) organoplatinum(II) complexes (Scheme 1) have
been employed to construct well-ordered supramolecular assem-
blies. For the mononuclear Pt(II) complexes, the intermolecular
Pt(II)–Pt(II) binding affinity is rather low (<10 kcal mol
1) [14],
which is not strong enough to drive the formation of long-range-
ordered assemblies. Accordingly, the elaborate choice of low-
steric ligands (such as halogen, acetylene, pyridine, etc.), together
with the synergistic incorporation of hydrogen bonds, facilitate
to enhance intermolecular complexation strength especially in
dilute solution. On the other hand, multidentate organoplatinum
(II) complexes possess large p-planar surface. Thanks to the con-
current participation of p–p stacking and Pt(II)–Pt(II) metal–metal
interactions, multidentate organoplatinum(II) complexes are
regarded as excellent building blocks for supramolecular assembly.
It should be noted that bottom-up assembling processes are
influenced by a number of intrinsic and extrinsic parameters. In
this regard, unravelling the assembling mechanism and pathway
is necessary to dictate the ordering of supramolecular nanostruc-
tures. Depending on the energy evolution of supramolecular
assembling processes, two different mechanisms can be divided,
namely isodesmic and cooperative mechanism [23–25]. For the
isodesmic mechanism, non-covalent forces involved in each of
the assembling step are identical to each other. In comparison,
the cooperative mechanism initiates with the nucleation step, fol-
lowed by the nonlinear growth of the elongated chain. As com-
pared to the isodesmic mechanism, the cooperative one avoids
the formation of small oligomers, and thereby favors for the forma-
tion of long-range ordered nanostructures with high degree of
polymerization value. In addition, pathway complexity also plays
a crucial role to determine organization and morphology of the
final nanostructures, by tailoring supramolecular assembly to the
 Y. Han et al. / Coordination Chemistry Reviews 414 (2020) 213300
thermodynamic equilibrium state or kinetic non-equilibrium state
[26–28].
The aim of this review is to highlight state-of-the-art progress
of organoplatinum(II)-based supramolecular assembling systems,
especially those developed in the recent ten years. Several elegant
reviews have already summarized spectroscopy and functionality
of organoplatinum(II)-based assemblies [14,15,17–22]. Neverthe-
less, few of them are focused specifically to long-range ordered
supramolecular nanostructures. To stimulate further research
activity in this area, herein the emphasis is paid to the molecular
design principles, which enable precise control over long-range
ordered supramolecular organization of organoplatinum(II) com-
plexes. For convenience of the detailed discussion, six major sys-
tems are catalogued by the supramolecular assembling modes
(Fig. 1). In addition, the applications of organoplatinum(II)-based
supramolecular nanostructures in sensing, emitting, semi-
conducting, bio-medical fields are briefly introduced.
2. Construction of organoplatinum(II)-based supramolecular
nanostructures
2.1. Primary self-assembly of monodentate Pt(II) complexes
Platinum(II) acetylides represent a typical type of monodentate
organoplatinum(II) complexes. In 2008, Schanze and coworkers
have reported a series of coil-rod-coil monomers (see compounds
1a–b in Fig. 2a) [29], consisting of platinum(II) acetylide as the
rigid rod and two tri(dodecyloxy)phenyl units on the periphery.
With the presence of rod–rod p–p stacking and rod–coil phase seg-
regation, these monomers aggregate in hydrocarbon solvents to
form supramolecular nanofibers and gels at room temperature
Fig. 1. Organoplatinum(II)-based long-range ordered nanostructures catalogued by
supramolecular assembling modes.
3
(Fig. 2a). The critical gelation concentration is approximately
1 mM in dodecane and hexane for both 1a and 1b. H-aggregation
of platinum(II) acetylides occurs during supramolecular assembly
process, as reflected by the obvious blue shift (~40 nm) in the
absorption spectra. Moreover, the platinum(II) acetylide com-
plexes are phosphorescent both in the solution and gel states. Tri-
plet energy transfer occurs when small amount of 1b (4 mol%) is
doped into supramolecular gels of 1a. It involves exciton diffusion
among 1a chromophores, followed by Dexter exchange energy
transfer to the trapped compound 1b. This work provides the first
example of triplet exciton diffusion and trapping in an
organoplatinum(II)-based supramolecular assembling system.
Platinum(II) acetylide-based supramolecular systems have been
also extensively studied by Yang, Xu, and coworkers [30–35]. A
series of linear-, triangular-, and rectangular-shaped monomers
are designed and synthesized. Intriguingly, various functional
groups such as iptycene, arene, porphyrin, and azobenzene have
been incorporated to the rigid platinum(II) acetylide units. Most
of the synthetic compounds exhibit high gelation efficiency in non-
polar hydrocarbon solvents. Moreover, honey comb-patterned
microporous films [31] and nanospheres [33] are fabricated for
some of the synthetic compounds under the specific conditions.
Despite the progress achieved, in-depth understanding of the
assembling mechanism involved in platinum acetylide-based sys-
tems have remained unexplored. Considering that natural assem-
bling systems such as microtubules and tobacco mosaic virus
tend to adopt cooperative nucleation–elongation mechanism, our
research group sought to mimic them and construct
organoplatinum(II)-based supramolecular assemblies via the same
mechanism. To attain this objective, the key strategy involves the
integration of two amide groups into rod-like platinum(II) acety-
lide unit (see monomers 2a–b in Fig. 2b). During the self-
assembly process, hydrogen bonding and p–p stacking interactions
are participated in a synergistic manner [36–40]. (S)-3,7-
dimethyloctyl groups are introduced into the peripheral side chain,
facilitating to induce a helical bias for the self-assembled struc-
tures (Fig. 2b). Accordingly, the supramolecular assembling pro-
cess can be quantitatively probed in apolar methylcyclohexane,
via the combination of circular dichroism (CD) spectroscopic mea-
surement and the mathematical analysis. Non-sigmoidal melting
curve is obtained (Fig. 2b), proving the involvement of cooperative
nucleation–elongation mechanism to form long-range ordered
supramolecular polymers.
Moreover, subtle change on the molecular structure exerts sev-
ere impact on the supramolecular polymerization behavior. For
example, the less bulky PMe3 and PEt3 substitution on platinum
(II) acetylide complexes are capable of forming single-handed
supramolecular fibers, while no aggregation is detected for the
counterpart complex with the bulky PBu3 substitution [37]. Poten-
tial applications of the resulting supramolecular nanostructures
are also exploited. For instance, the [4+2] endoperoxidation is trig-
gered by irradiating 2a under 460 nm LED, whilst the backward
deoxygenation reaction proceeds upon standing at room tempera-
ture [39]. Fluorescent anti-counterfeiting QR codes are further fab-
ricated for supramolecular polymers of 2a via the inkjet-printing
technique. Thanks to the reversible photo-responsiveness, the
embedded information in QR codes can be reversibly erased and
restored with fast response and ease of operation (Fig. 2b).
As compared to the above platinum(II) phosphine complexes,
platinum(II) pyridine complexes possess low steric hindrance.
Accordingly, they are also employed as the primary building blocks
to construct well-ordered nanostructures [41–43]. In this respect,
Fernández and coworkers have designed and synthesized com-
pound 3a (Fig. 3). It is capable of assembling into nanofibers in
methylcyclohexane via the cooperative nucleation–elongation
mechanism [44]. Remarkably, 3a adopts slipped arrangement for
4 Y. Han et al. / Coordination Chemistry Reviews 414 (2020) 213300

Fig. 2. (a) Structures of 1a–b, and phosphorescent gel of 1a in dodecane (c = 1 mM). (b) Graphic representation for the cooperative supramolecular polymerization of 2a–b.
Bottom-left, variable-temperature CD spectra of 2a in methylcyclohexane, and the corresponding non-sigmoidal melting curve (inset); bottom-right, photographs of the
fluorescent QR code (size: 4  4 cm on paper) from 2a and its photo-responsiveness. Reproduced with permission of 2008 American Chemistry Society from ref. [29], and
2018 Nature Publishing Group from ref. [39].

the neighboring monomers in the self-assembled state (Fig. 3). It
involves p-stacking of four out of six aromatic rings, together with
several weak intermolecular interactions such as CAH---p,
C„C---Pt, and CAH---Cl forces (Fig. 3). In terms of the amphiphilic
monomer 3b (Fig. 3), it is prone to self-assemble into deep yellow
gels in alcohols (MeOH, EtOH, n-BuOH) and water [45]. In the
self-assembled structures, 3b also packs in a slipped fashion. As
evidenced by X-ray diffraction of 3b, multiple CAH---Cl and
Fig. 3. Structure of 3a–b, and energy-minimized geometry for the tetramer of 3a
obtained via semi-empirical PM6 calculation. Reproduced with permission of 2016
Wiley-VCH Verlag GmbH from ref. [44].
CAH---p forces, along with CAH---O interactions between the
peripheral triethylene glycol chains of two different molecules,
stabilize the aggregated structure.
2.2. Primary self-assembly of multidentate Pt(II) complexes
Multidentate Pt(II) complexes, especially platinum(II) polypyri-
dine complexes, are capable of generating Pt(II)–Pt(II) metal–metal
interactions upon supramolecular aggregation. The process is com-
monly accompanied by the dramatic spectroscopic changes. Hence,
these complexes have been widely exploited for the fabrication of
long-range ordered supramolecular nanostructures. Yam’s group
has pioneered the self-assembly study of platinum(II) terpyridine
[Pt(terpy)] complexes. In their early study, they have reported
the polymorphism phenomena (dark green color versus red color
of the single crystals) of [Pt(terpy)(C„CAC„CH)]OTf (OTf = tri
fluoromethanesulfonate) crystals [46]. Short intermolecular Pt-Pt
distance of 3.388 Å exists for the dark green crystal form, denoting
the presence of strong Pt(II)–Pt(II) metal–metal interactions.
On this basis, Yam and coworkers sought to construct
supramolecular metallogels, by attaching tris-dodecyl hydrocar-
bon chains on the periphery of alkynylplatinum(II) terpyridine unit
(Fig. 4a) [47–49]. For monomer 4a (Fig. 4a), it is prone to form clear
gel in organic solvents such as dodecance and DMSO (critical gela-
tion concentration: 4.4 mg/mL in DMSO; Tgel = 55 °C). Drastic color
change from purple to orange occurs for 4a during gel-to-sol tran-
sition process. It originates from the presence/absence of Pt(II)–Pt
(II) metal–metal interactions during supramolecular aggregation/
de-aggregation processes. Interestingly, the gelation process can
be modulated by structural variation at the molecular level. For
example, 4b (Fig. 4a) with three tert-butyl substituents on the ter-
pyridine ligand forms less stable metallogels, as reflected by its
 Y. Han et al. / Coordination Chemistry Reviews 414 (2020) 213300
Fig. 4. (a) Gelation behaviors of 4a–c in DMSO. (b) Structures of 5a–b, and the solvato-chromic behavior of 5a. (c) Unusual emission enhancement phenomenon during the
gel-to-sol phase transition of 6. Reproduced with permission of 2007 Royal Society of Chemistry from ref. [48], 2007 Wiley-VCH Verlag GmbH from ref. [51], and 2009
American Chemistry Society from ref. [53].
higher critical gelation concentration (7.8 mg/mL) and lower sol–
gel transition temperature (Tgel = 45 °C) than those of 4a. The result
is ascribed to the absence of Pt(II)–Pt(II) metal–metal interactions
for the 4b self-assembly process, since the steric bulky tert-butyl
substituents greatly hinder Pt centers from closely proximity. In
addition, 4a and 4c (Fig. 4a) display distinct color for the metallo-
gel [purple for the OTf salt versus deep red for the PF6 (hexafluo-
rophosphate) salt, Fig. 4a]. Hence, counter-anion variation
governs the extent of Pt(II)–Pt(II) and p–p interactions involved
in the gelation process. In addition, Yi and coworkers have
designed cholesterol-appended Pt(terpy) gelators, which form
stable metallogels in alcohol, ethyl acetate and toluene upon son-
ication [50].
Hydrogen bonds provide the additional stabilization factor for
Pt(terpy)-based supramolecular assemblies. Ziessel and coworkers
have attached Pt(terpy) to a 3,5-diacylamido framework (see
monomers 5a-b in Fig. 4b) [51]. The amide units in 5a-b are
expected to strengthen intermolecular association via intermolec-
ular hydrogen bonds. The resulting systems display solvato-
chromic properties, by reversibly converting among the mono-
meric, oligomeric and polymeric states (Fig. 4b). TEM and AFM
measurements confirm the presence of linear fibrils with lengths
of several hundred nanometers in the dodecane gels (critical gela-
tion concentration = 7.5 mmol/L). Pt(II)–Pt(II) metal–metal interac-
tions are involved in the gelation state, as reflected by the deep-
green color and near-infrared emission at 830 nm. For 5b with
the branched alkyl chains on the periphery, it tends to form hexag-
onal 2D lattice mesophases. Besides, Yam’s group has also reported
Pt(terpy) complex with the L-valine-modified alkynyl ligand [52].
The compound is capable of forming gel in acetonitrile (critical
gelation concentration = 2.5 mg/mL), attributed to the cooperative
participation of Pt(II)–Pt(II), p–p, and hydrogen bonding
interactions.
Generally, Pt(terpy) complexes suffer from low emission inten-
sity in fluid solution, because of the involvement of non-radiative
d–d deactivation pathway [1]. To address this issue, a feasible
strategy is to replace terpyridine by the 2,6-bis(N-alkylbenzimida
zol-20 -yl)pyridine (bzimpy) analogue. Triplet intra-ligand (IL) p–
p* emission of the bzimpy ligand is lower-lying in energy than that
of terpyridine, thus giving rise to the highly emissive character. On
this account, Yam’s group has designed a novel type of emissive
5
supramolecular gels on the basis of monomer 6 (Fig. 4c) [53].
Intriguingly, 6 shows emission enhancement during the gel-to-
sol phase transition upon increasing the temperature. This unusual
behavior is rarely encountered, which is in stark contrast to the
conventional thermotropic luminescent gels. The unique phe-
nomenon is ascribed to heating-induced increase in the degrees
of freedom and motion, which consequently increase the excimer
population. Luminescence quantum yield of the excimeric excited
state is likely to be much higher than that of the IL excited state,
leading to a strongly luminescent sol form than the gel form of 6.
Supramolecular assembly has also been investigated for other
tri- and bi-dentate platinum(II) complexes [54–57]. For example,
our research group has replaced alkynyl Pt(terpy) by the isoelec-
tronic platinum(II) 6-phenyl-2,20 -bipyridine isocyanide complex
[58]. An obvious solvochromic phenomenon occurs during the
reversible assembling process, with yellow-green emission in the
monomeric state and red-emission in the aggregated state. Assem-
bling organoplatinum(II) complexes can be also proceeded in aque-
ous media [59–61]. For example, De Cola et al. have designed
neutral platinum(II) 1,3-di(2-pyridine)-benzene complexes, which
bear hydrophilic oligo-ethylene glycol chains to increase the water
solubility. The designed amphiphilic molecules tend to aggregate
to phosphorescent hydrogels, by utilizing host–guest interactions
between cyclodextrins and the oligo-ethylene glycol tail of
organoplatinum(II) complexes [59]. Moreover, the resulting
supramolecular nanostructures exhibit a high cell permeability
and low cytotoxicity, which is promising for long-lived bio-
imaging application [60].
In addition to the above mononuclear cyclometallated platinum
(II) systems, supramolecular assembly can also take place for the
multinuclear platinum(II) complexes [62–65]. Yam’s group has
reported an elegant example, in which dinuclear Pt(terpy) are teth-
ered by oligo(para-phenylene ethynylene)s unit [63]. Two hydro-
philic triethylene glycol and two hydrophobic octadecane chains
are attached to the rigid segment, endowing amphiphilic character
to the resulting monomers 7a–b (Fig. 5a). Notably, 7a tends to
aggregate into tubular architecture in DMSO, with a uniform diam-
eter of ~13.0 nm and length of 2.0–5.5 lm (Fig. 5a). In stark con-
trast, 7b, bearing tert-butyl units on one of the terpyridine unit,
is prone to form helical ribbons with the diameter of ~9.5 nm
and 0.7–2.1 lm in length (Fig. 5a). Presumably, presence of steric
6 Y. Han et al. / Coordination Chemistry Reviews 414 (2020) 213300
Fig. 5. (a) Supramolecular assembly of 7a and 7b into nanotubes and helical nanoribbons in DMSO, respectively. (b) Distinct supramolecular assembly mechanisms for
monomers 8a–c. Reproduced with permission of 2016 National Academy of Sciences from ref. [63], and 2018 American Chemistry Society from ref. [64].
Fig. 6. Ultrasound-induced sol-to-gel phase transition of clothespin-shaped molec-
ular 9. Reproduced with permission of 2011 American Chemical Society from ref.
[66] and 2019 Wiley-VCH Verlag GmbH from ref. [67].
bulky tert-butyl groups on 7b restricts the formation of directional
Pt(II)–Pt(II) metal–metal interactions, and thereby influences the
final morphologies of the self-assembled nanostructures.
In an extensive study, the same group has designed dinuclear
platinum(II) bzimpy monomers 8a–c (Fig. 5b) [64]. The overall
hydrophilicity/hydrophobicity are adjusted, by introducing the
peripherical hydrocarbon chains with the different length. For
monomer 8a with the shortest hydrophobic chains, it undergoes
isodesmic mechanism for the self-assembly process (Fig. 5b). Upon
increasing the alkyl lengths from AC6H13 to AC12H25 (monomer
8b), self-assembly follows the cooperative nucleation–elongation
mechanism (Fig. 5b). Nevertheless, it switches back to the isodes-
mic one, when the hydrophobic chains are further prolonged
(monomer 8c, Fig. 5b). Hence, variation of the peripheral alkyl
chains exerts a profound influence on the supramolecular assem-
bling mechanisms.
Additionally, Naota and co-workers have reported a chiral,
clothespin-shaped dinuclear trans-bis(salicylaldiminato) Pt(II)
complex 9 (Fig. 6) [66,67]. The compound is non-emissive in
organic solvents such as cyclohexane. Nevertheless, upon ultra-
sound sonication for a few seconds, hetero-chiral, interpenetrative
dimeric structure generates, further leading to the formation of
supramolecular polymers and phosphorescent gels (Fig. 6). The
gels convert back to the solution state after heating above Tgel.
Emission signal of the supramolecular gels can be further con-
trolled by sonication time, linker length, and optical activity of
the complexes. This intriguing example represents a remote and
instant control over the supramolecular gelation processes.
2.3. Hierarchical assembly of Pt(II) complexes
Hierarchical assembly is regarded as an important route toward
complex supramolecular systems [68]. Generally, the hierarchical
process relies on the construction of a pre-assembled
structural motif, which further assembles through the additional
 Y. Han et al. / Coordination Chemistry Reviews 414 (2020) 213300 7

non-covalent forces. Foldamers mimic the secondary structures of
proteins and nucleic acids, which are appealing helical scaffolds for
the hierarchical supramolecular assembly. In this respect, Yam and
coworkers have previously prepared a series of dinuclear Pt(terpy)
complexes connected by the oligomeric m-phenylene ethynylene
(m-OPE) linker [69]. The synthetic compounds can fold back onto
themselves in an intramolecular manner, giving rise to the forma-
tion of short helical strands. The folding process is mediated by
changing the solvent from CHCl3 to CH3CN. When the acid-
sensitive oligo(ethynyl-pyridine) is incorporated as the spacer
instead of m-OPE, the reversible switching from transoid to cisoid
forms can be manipulated with multi-stimuli responsiveness
[70]. On this basis, it is fascinating to develop higher-order hierar-
chical nanostructures, by employing helical foldamers as the pre-
assembled intermediate.
To achieve this goal, Yam’s group has further designed com-
pound 10 (Fig. 7a). The tridentate bzimpy units on 10 serve as
the pincer ligands, while the pentameric m-OPE acts as the foldable
linker [71]. Thanks to the presence of four dodecyl chains, it facil-
itates rod-coil phase segregation between the inner single-turn fol-
damer and the peripheral flexible chains. Accordingly, high-order
hierarchical architectures are prone to form in acetonitrile via
intra- and inter-molecular Pt(II)–Pt(II) metal–metal and p–p stack-
ing interactions. The hierarchical assembling process of 10 adopts
the cooperative nucleation-elongation mechanism. Depending on
Meijer–Schenning–van-der-Schoot mathematical model [24], the
enthalpy release upon elongation (he) and critical elongation tem-
perature (Te) are calculated to be
117.1 kJ mol
1 and 318 K,
respectively. The number-averaged degree of polymerization value
for 10 is calculated to be 1500 at room temperature. Ultimately,
orange-colored metallogel forms, because of the reciprocal associ-
ation of multiple helices. It should be mentioned that the m-OPE
spacer length is critical for the hierarchical assembly processes.
For the structurally similar compound with the tetrameric m-OPE

Fig. 7. (a) Graphic representation for the hierarchical assembly of 10. (b) Graphic representation for the hierarchical assembly of (R)-11 and (S)-11. Right bottom, CD spectral
changes of (R)-11 upon increasing the water content in CH3CN. (c) Dynamic switching of 12 with distinct emission color changes. Reproduced with permission of 2017
American Chemistry Society from ref. [71], 2013 Royal Society of Chemistry from ref. [72], 2019 National Academy of Sciences from ref. [73].
8 Y. Han et al. / Coordination Chemistry Reviews 414 (2020) 213300
linker, intramolecular folding of the two terminal platinum(II)
bzimpy moieties is restricted. As a consequence, it fails to gelate
in CH3CN under the same circumstances.
Later on, Yam and coworkers have designed two enantiomers
(S)-11 and (R)-11 (Fig. 7b) [72]. The presence of two hydrophilic tri-
ethylene glycol monomethyl ethers facilitates the hierarchical
assembly in aqueous medium. Thanks to the presence of chiral
binaphthol unit, the folding and hierarchical assembling processes
can be directly monitored via CD spectroscopy. Upon increasing the
water/acetonitrile volume ratio, (R)-11 exhibits an extraordinary
growth of the Cotton effect, reaching a maximum at 70% water in
the high-energy region (271–340 nm, Fig. 7b). The progressive
increase of CD intensity for (R)-11 reflects the formation of helically
stacked array of M-helices. There is a slight increase in the CD signal
in the region of the MMLCT transition tail at 430 nm (Fig. 7b), sug-
gesting the participation of Pt(terpy) moieties for the hierarchical
assembly process. In terms of (S)-11, its CD spectrum exhibits a mir-
ror image relationship to that of (R)-11 under same conditions.
Fibril-like assemblies are observed for both (S)-11 and (R)-11, with
the length of 2.0–2.5 lm and width of 130–480 nm. Therefore, hier-
archical assembly through the reciprocal association of multiple
helices leads to the formation of supramolecular columns.
Very recently, the same group has constructed another type of
platinum(II)-based hierarchical assemblies, which display drastic
phosphorescent emission color changes. The design principle relies
on the molecular hinge 12 (Fig. 7c) [73]. The use of rigid butadiynyl
linker as the rotating axis, together with the incorporation of
cyclometalated organoplatinum(II) moieties as the flaps, leads to
the stabilization of 12 in the closed form in CH2Cl2. This state is
mainly stabilized by intra-molecular p–p stacking interaction
between the organoplatinum(II) pincers, leading to the deep-red
emission in CH2Cl2. Upon increasing the amount of apolar hexane,
the red emission band gradually declines (kmax = 690 nm in
CH2Cl2), accompanied by the emergence of green emission
(kmax = 516 nm in hexane/CH2Cl2 = 9/1). The green emission orig-
inates from triplet intra-ligand excited state. The signal illustrates
the predominance of the open form of 12, which hierarchically
aggregates via intermolecular stacking. In addition to solvent vari-
ation, the reversible close-to-open conformational changes can be
also regulated upon heating/cooling.
Fig. 8. (a) UV–Vis absorption and color changes of 13 upon varying water/acetone volume ratio. TEM images demonstrate the morphological change from vesicle to
nanofibers upon increasing the acetone content. (b) Solution color changes of 14 upon increasing the content of water in THF. TEM images show the change from nanoring to
nanofibers upon increasing the water content. Reproduced with permission of 2011 American Chemistry Society from ref. [81], and 2014 American Chemistry Society from
ref. [82].
Yang and co-workers have also performed systematic studies
on hierarchical self-assembly of organoplatinum(II) moieties [74–
80]. In their design, metal-coordination macrocycles and cages
are initially formed as the pre-assembled motif in CH2Cl2. When
platinum(II) bzimpy units are attached on the periphery, hierarchi-
cal self-assembly takes place upon gradual addition of apolar
cyclohexane, as driven by metallophilic Pt–Pt, p-p stacking and
hydrophobic interactions. The resulting metallogels are collapsed
upon addition of electron-rich coronene, because of the presence
of competitive donor–acceptor interactions between coronene
and alkynylplatinum(II) bzimpy units [74]. In another related
study, the same group has found that the platinum(II) bzimpy-
based assemblies feature intriguing chromic behaviors upon selec-
tive absorption of CH2Cl2 vapor [75].
2.4. Assembly of Pt(II) complexes into diverse morphologies
Supramolecular assembly process is primarily governed by the
combination of various non-covalent driving forces. With the del-
icate balance of these non-covalent bonds, it is feasible to obtain
diverse morphologies under different conditions. For example,
Yam and co-workers have designed a negatively-charged Pt(bz-
impy) complex 13 (Fig. 8a), consisting of two pendant sulfonate
units [81]. Notably, the solvation conditions have a profound
impact on the final morphologies of supramolecular nanostruc-
tures. In 1:1 water/acetone (v/v), the monomeric species domi-
nates, as manifested by the absence of MMLCT bands in both
UV–Vis and emission spectra (Fig. 8a). Increase of either acetone
or water content leads to the appearance of MMLCT absorption
bands (Fig. 8a), suggesting the existence of supramolecular aggre-
gation. Nevertheless, the assembling scenario is a little different in
both media. Specifically, upon increasing the water content, 13
tends to assemble into bilayered vesicular structures (Fig. 8a). It
is likely that charged sulfonate groups are pointing outward in
water, whilst the hydrophobic Pt(bzimpy) moieties pack together
to avoid unfavorable contact with water. On the other hand, in
9:1 acetone:water (v/v), the sulfonate groups are no longer well
solvated. As a consequence, the sulfonate ionic heads start to
aggregate and pull the complexes into close proximity, leading to
 Y. Han et al. / Coordination Chemistry Reviews 414 (2020) 213300 9

their aggregation into nanofibers (Fig. 8a). More interestingly, mor-
phological transformation is accompanied by the variation of opti-
cal signals. The red color in aqueous solution, together with the
blue color in 9:1 acetone:water (v/v), are distinct from that in
the monomeric state (yellow color in 1:1 acetone:water, v/v), as
directly visualized by the naked eye (Fig. 8a).
Later on, the same group has designed an amphiphilic Pt(terpy)
complex 14 (Fig. 8b) [82], which also assembles into diverse nanos-
tructures under different solvation conditions. The key design prin-
ciple lies in the presence of hydrophobic polyhedral oligomeric
silsesquioxanes (POSS) unit on 14. In pure THF, 14 is in the molec-
ularly dissolved state. With the gradual addition of water into THF
(water/THF: 30/70, v/v), 14 aggregates into nano-ring structure
(Fig. 8b). It is primarily governed by the hydrophobic–hydrophobic
interactions between the neighboring POSS scaffolds. When the
water content further increases (water/THF: 70/30, v/v), the mor-
phology converts from nano-rings to nano-rods (Fig. 8b). It is
accompanied by the emergence of low-energy MMLCT spectro-
scopic bands. Unambiguously, the organoplatinum(II) complexes
pack together in a head-to-head manner, with the participation
of directional metallophilic interactions. Therefore, the subtle
interplay of Pt(II)–Pt(II) metal–metal, p–p stacking, and
hydrophobic-hydrophobic interactions are responsible for the
morphological transformation.
Besides, Bu and coworkers have also reported morphological
transformation of organoplatinum(II)-based supramolecular sys-
tems [83–89]. In their design principles, organoplatinum(II) com-
plexes are covalently attached to flexible polymers such as
polystyrene. It is found that solvent polarity exerts crucial impact
on the morphologies of the resulting assemblies. Briefly, free-
standing bilayered sheets are formed in toluene/methanol solvent
(v/v = 33/67), as evidenced by TEM and HAADF-STEM experiments.
When the methanol content further increases to 90 vol%, the bilay-
ered nanosheets convert into core-corona micelles, with the diam-
eter of 25–80 nm [87]. Such morphological transformation is
primarily ascribed to the solvophobic effects of hydrophobic poly-
styrene in methanol.
2.5. Pathway complexity in assembling Pt(II) complexes
Supramolecular nanostructures described in the above sections
are primarily in the thermodynamic equilibrium state. Besides,
pathway complexity can be also involved in the organoplatinum
(II)-based supramolecular assembly process. As a consequence,
both equilibrium thermodynamic and non-equilibrium kinetic
products form under same conditions. For example, Rybtchinski
and co-workers have reported pathway-dependent supramolecu-
lar assembly via the solvent processing technique [90]. The
designed amphiphile 14 contains perylene diimide/Pt(terpy) core,
along with PEG and tripeptide on each of the end (Fig. 9a). At high
water content (water/THF = 95:5, v/v), 14 assembles into disor-
dered curved fibers due to the existence of strong hydrophobic

Fig. 9. (a) Graphic illustration of different morphologies obtained by diluting a water/THF = 80/20 mixture of 14 to 95/5 at different evolution times during self-assembly (0,
45, and 2400 min). (b) Illustration of the landscape for supramolecular assembly of 15, along with the snapshots of time-dependent morphologies. (c) Graphic representation
for precise control over the length of supramolecular nanofibers assembled from 16 via the seeded growth approach. Reproduced with permission of 2011 Wiley-VCH Verlag
GmbH from ref. [90], 2015 Nature Publishing Group from ref. [91], and 2015 Royal Society of Chemistry from ref. [93].
10 Y. Han et al. / Coordination Chemistry Reviews 414 (2020) 213300
interactions. Simultaneously, a weak CD signal appears, which
does not evolve over time. It is rationalized that supramolecular
aggregates are in the kinetic-trapped state, which fails to convert
into the thermodynamic state because of the slow assembly/disas-
sembly dynamics. Upon increasing the THF percentage (water/
THF = 80/20, v/v), CD signal of the as-prepared solution increases
with time, leading to the formation of straight fibers after three
days. Obviously, the good solvent, THF, attenuates the solvophobic-
ity, providing the metastable assemblies which can equilibrate to
the thermodynamic product. On this basis, a water/THF = 80/20
(v/v) solution of 14 is prepared and allowed to evolve for 0 min,
45 min or 2400 min, followed by dilution with water to 5% THF
content. Despite the equal solvent composition under the final con-
ditions (95:5 water/THF, v/v, c = 1  10
4 M), distinct assemblies
such as short curved fibers, long fibers and nanotubes are obtained
(Fig. 9a), which do not interconvert for at least two months.
Besides, De Cola and co-workers have reported an elegant
example, which is capable of evolving from kinetic metastable to
thermodynamic states over time [91,92]. For the designed triden-
tate platinum(II)-based amphiphile 15 (Fig. 9b), it initially aggre-
gates into a kinetically metastable state (state A, Fig. 9b) in
water/1,4-dioxane. For the resulting nanoparticles, hydrophilic
flexible tails are solvated in the highly polar medium, while the
hydrophobic platinum(II) complexes pack tightly in the inner core.
The orange phosphorescent emission of state A suggests the forma-
tion of tight Pt(II)–Pt(II) metal–metal interactions. Intriguingly,
after standing at room temperature for three weeks, state A con-
verts to the thermodynamically stable state (state C, Fig. 9b) with
the blue emitting character. The thermodynamic state exhibits
micrometer long ribbon-like structures. The conversion process
from the kinetic to thermodynamic states is rather slow, which
can be sped up by increasing the volume of 1,4-dioxane in water.
Detailed kinetic studies reveal the presence of a transient state
(state B, Fig. 9b) during the A-to-C conversion process. It emits
green phosphorescence, suggesting the presence of Pt(II)–Pt(II)
metal–metal interactions with slightly longer distance than that
of state A. With the confocal fluorescence microscopic imaging
Fig. 10. Graphic representation for pathway complexity of compounds 17–18 during the self-assembly processes. Bottom right, variable temperature UV–Vis spectral changes
of 17 upon cooling. Reproduced with permission of 2019 Wiley-VCH Verlag GmbH from ref. [95].
technique, the three different types of supramolecular assemblies
can be visualized in real time.
On this basis, Manners and coworkers have prepared another
amphiphile 16 (Fig. 9c) [93,94]. The pyridine ancillary ligand with
a long poly(ethylene glycol) (PEG16) chain could not only enhance
the solubility, but prevent inter-chain packing at the fiber core.
Accordingly, polydisperse rod-like structures are prepared, in
which the diameter is closer to the diameter for a single
supramolecular polymer chain. They have further explored
‘‘seeded growth approach” to achieve accurate control over the
length and morphology of the assembling structures. Briefly, small
seed fibers are prepared in chloroform under the sonication condi-
tion. Further addition of 16 into the seeded fibers (number-average
contour length: 60 nm) in acetonitrile leads to the formation of
uniform nanofibers with relatively narrow length distributions
(number-average contour length: 390 nm; length distribution:
1.21). The fibers remain colloidally stable in solution for at least
6 months, while no significant changes in the length and length
distribution are observed over 3 days. Hence, seeded growth
method suppresses the dynamic exchanging of unimers. Such
kinetic controlled processes facilitate to provide well-ordered
supramolecular nanostructures.
Pathway complexity is also encountered for monodentate Pt(II)
complexes during the supramolecular assembly processes. In this
respect, Fernández and coworkers have prepared an amphiphilic
monomer 17 (Fig. 10), which is unsymmetrically substituted with
triethyleneglycol and dodecyloxy side chains [95]. 17 undergoes
self-aggregation upon cooling its methylcyclohexane solution from
353 K to 303 K. Weak coupling of the p-scaffold suggests the for-
mation of slipped arrangement (state A, Fig. 10), which is similar
to those of the aforementioned compounds 3a–b (Fig. 3). At this
stage, discoidal nanoparticles are observed with the size between
20 and 60 nm, suggesting the involvement of anti-cooperative
mechanism. Intriguingly, further cooling the methylcyclohexane
solution of 17 to 283 K leads to a pronounced spectral change
(8 nm red shift of kmax, Fig. 10). It indicates the formation of
pseudo-parallel arrangement (state B, Fig. 10), with less pro-
 Y. Han et al. / Coordination Chemistry Reviews 414 (2020) 213300
nounced translational displacement for the neighboring monomers
than that of state A. For state B, fiber networks of several micro-
meters in length are observed, demonstrating the cooperative
supramolecular polymerization of 17 into long 1D nanostructures.
Hence, the buffering of monomers into anti-cooperative assemblies
may open up a new strategy for the pathway control of
organoplatinum(II)-based nanostructures. In a related study, the
same group has found that the two competing states [slipped (A)
vs pseudo-parallel (B)] do not interconvert over time in a period
of at least six months for monomer 18 (Fig. 10) [96]. With the pre-
cise controlling of cooling rate and concentration, both states can
be isolated concomitantly in the same solution. The phenomenon
is in close resemblance to polymorphism encountered in the
crystals.
2.6. Multi-component co-assembly of Pt(II) complexes
As compared to mono-component self-assembly, multi-
component co-assembly is considered as an efficient protocol
toward complexed supramolecular systems. In this context, Che
and co-workers have successfully constructed supramolecular
cross-linked networks and hydrogels, by co-assembling mono-
and di-nuclear platinum(II) compounds together (see 19 and 20
Fig. 11) [97]. Remarkably, the length of flexible oligo(oxyethylene)
chain on 20 exerts a crucial impact on the gelation capability in
aqueous media. In detail, the long bridging chain (n = 76 for 20a)
is capable of maintaining unfolded conformation, which facilitates
intermolecular connection of supramolecular nanofibers derived
from 19. Hence, adding 2.0 wt% of 20a into the aqueous solution
of 19 results in the spontaneous formation of hydrogels with bright
red emission. On the contrary, the ditopic cross-linker 20b with
short oligo(oxyethylene) chain prefers to adopt folded conforma-
tion. It fails to form hydrogels with 19, due to the lack of efficient
intermolecular crosslinking.
Fig. 11. Graphic representation for supramolecular co-assembly between 19 and 20 to form hydrogels. Reproduced with permission of 2014 Royal Society of Chemistry from
ref. [97].
11
Co-assembly can also take place between two different types of
organoplatinum(II) complexes. In this context, Magnus’ green salt,
[Pt(NH3)4][PtCl4], is regarded as a prototype [98]. In the crystal of
Magnus’ green salt, the oppositely charged platinum(II) complexes
form alternating chains via electrostatic and Pt(II)–Pt(II) metal–
metal interactions. Inspired by this fascinating structure, much
efforts have been devoted toward multi-component
organoplatinum(II)-based co-assemblies. For example, Che’s group
has designed two distinct organoplatinum(II) monomers, namely
the neutral species 21 and the cationic species 22 (Fig. 12a)
[99,100]. Nanowires prefer to form upon mixing equimolar amount
of 21 and 22 together in the concentrated acetone, accompanied by
the emergence of a new absorbance in the range of 604–615 nm.
The newly-formed band is assigned to MMLCT transitions, demon-
strating the involvement of intermolecular Pt(II)–Pt(II) metal–
metal interactions. Upon further replacing chloride on 21 by the
acetonitrile ligand, morphology of the co-assembled structure
undergoes a nanowire-to-nanowheel metamorphism process
(Fig. 12a). Higher reaction temperatures (up to 70 °C) and excess
amount of NH4PF6 facilitate to the formation of nano-wheel struc-
tures. Hence, the fascinating co-assembled supramolecular sys-
tems feature ligand-triggered morphological evolution character.
Our research group has also developed supramolecular alter-
nate co-assemblies via the synergistic participation of Pt(II)–Pt(II)
metal–metal interactions [101,102]. Specifically, positively-
charged Pt(terpy) complex 23 is designed as the acceptor monomer
(Fig. 12b). It self-assembles in apolar methylcyclohexane/1,2-dich
loroethane (95:5, v/v) through intermolecular p–p stacking and
van der Waals interactions. As a result, one-dimensional nanofi-
bers form via nucleation–elongation cooperative mechanism. It is
worthy to note that, due to the presence of sterically bulky tert-
butyl units, Pt(II)  Pt(II) metal–metal interactions are ruled out
for the 23 mono-component self-assembly process (Fig. 12b).
When the neutral monomer 24 (Fig. 12b) is added into 23 in
methylcyclohexane/1,2-dichloroethane (95:5, v/v), intermolecular
12 Y. Han et al. / Coordination Chemistry Reviews 414 (2020) 213300

Fig. 12. (a) Graphic representation for the nanowire-to-nanowheel metamorphism process of co-assembly 21/22 via the ligand-substitution reaction. (b) Graphic
representation for the formation of supramolecular alternate co-assembly 23/24, because of the participation of Pt(II)  Pt(II) metal–metal interactions for the hetero-
complexation process. Reproduced with permission of 2008 Wiley-VCH Verlag GmbH from ref. [99], and 2018 Royal Society of Chemistry from ref. [101].

donor–acceptor interactions are prone to form due to their similar
p-surfaces. Meanwhile, the reduced steric hindrance between 23
and 24 gives rise to the formation of Pt(II)–Pt(II) metal–metal
interactions (Fig. 12b), which prevails the hetero-complexation
strength over the homo-complexation one. As a consequence, the
alternate arrangement exists as the thermodynamic stable state
for co-assembly 23/24, with the appearance of MMLCT absorption
band between 550 and 700 nm. Such an ‘‘emergence upon co-
assembly” property is further applied for red-light irradiated oxi-
dation of a-terpinene to ascaridole, which is unattainable for each
of the individual species. By utilizing the similar concept, Yam and
coworker have also realized two-component organoplatinum(II)
co-assemblies in aqueous solution [103].
Very recently, our research group has further developed a tern-
ary co-assembled system in aqueous medium, consisting of
positively-charged Pt(terpy) complexes 25a–b and neutral gold
(III) amphiphile 26 (Fig. 13) [104]. The purpose of the ternary co-
assembled system is to construct artificial light-harvesting systems
with high triplet energy transfer efficiency. In general, several chal-
lenges need to be addressed to realize triplet energy transfer in
water. Specifically, the phosphors should be shielded from water
and molecular oxygen, which facilitate to maintain intense emis-
sion intensity. Moreover, the donor–acceptor phosphors should
be organized in close proximity, yet simultaneously avoiding direct
homo- and hetero-interactions to minimize the potential energy
losses. To meet these requirements, 26 is employed as the com-
partmentalized agent. Considering the presence of non-emissive
gold(III) headgroup and hydrophilic polyethylene glycol tail, 26
tends to assemble into micelles in water, which render synergistic
rigidifying and hydrophobic shielding effects to the platinum(II)
terpyridine complexes. Accordingly, it gives rise to enhanced phos-
phorescent emission of the platinum(II) complexes 25a (or 25b) in
aqueous environment. More importantly, the 25a-26 (or 25b-26)
hetero-complexation prevails over the homo-complexation ones,
ascribed to the strong p-stacking strength between neutral gold
(III) headgroup on 26 and positively-charged platinum(II) phos-
phors 25a–b. As a result, the two platinum(II) phosphors are den-
sely packed, yet separately partitioned via the compartmentalized
agent 26. Highly efficient light harvesting and energy transfer can
be realized in aqueous medium (Fig. 13), by taking advantage of
triplet exciton stabilization and ordered spatial organization for
D-A phosphors 25a–b. Therefore, the compartmentalization effect
involved in the ternary co-assembled system strategy provides a
feasible approach toward color-tunable phosphorescent nanoma-
terials in aqueous media.
2.7. Hybrid co-assembly with the presence of Pt(II) complexes
As discussed in Section 2.6, supramolecular co-assembly takes
place between structurally similar organoplatinum(II) compounds.
Besides, co-assembly can be also realized for structurally dissimilar
components, by programming directional non-covalent bonds
 Y. Han et al. / Coordination Chemistry Reviews 414 (2020) 213300
Fig. 13. Graphic representation for the triplet energy transfer of ternary
co-assembly 26/25a/25b in aqueous environment. Reproduced with permission of
2019 Nature Publishing Group from ref. [104].
between organoplatinum(II) complexes and the complementary
agents. For example, electrostatic interactions exist between
positively-charged alkynyl Pt(terpy) and negatively-charged poly-
electrolyte such as poly(acrylic acid) carboxylate. Yam’s group
has proposed the ‘‘polyelectrolyte-induced assembly” concept, by
taking advantage of multivalent electrostatic forces between
organoplatinum(II) complexes and the anionic polymer [84,105].
Simultaneously, MMLCT bands appear due to the presence of Pt
(II)–Pt(II) metal–metal interactions in the co-assembled structure.
In recent years, the same group has employed poly(ethylene
glycol)-b-poly(acrylic acid) (PEG45-b-PAA69) as the co-assembled
Fig. 14. Graphic representation for conversion from the kinetically trapped nanofibers to thermodynamically stable nanobelts upon sonicating co-assembly 27/PEG45-b-
PAA69. Reproduced with permission of 2017 Elsevier Sciencedirect from [107].
13
species [106–108]. The PAA block is capable of neutralizing the
cationic Pt(terpy) 27 (Fig. 14). In the meantime, the PEG blocks
not only provide excellent solubility in the mixture of
acetonitrile-methanol–water (1:1:8, v/v/v), but play a crucial role
in inhibiting the growth of nanostructures in transverse direction.
Accordingly, uniform core–shell nanofibers are obtained for
27/PEG45-b-PAA69 co-assembly as the kinetically trapped product
(Fig. 14). Inside the nanofibers, cylindrical core is formed by PAA
blocks and hexagonally packed molecular columns of 27 along
the fiber long axis. Either sonication or thermal annealing disrupts
the core–shell nanofibers, and thereby leads to the formation of
short patchy nanofibers (Fig. 14). The side and end patches direct
transverse and longitudinal self-assembly of the short patchy
nanofibers to form core–shell nanobelts as the thermodynamically
stable state (Fig. 14) [107,108]. On this basis, it is also
capable of constructing segmented heterojunction materials, by
co-assembling different type of organoplatinum(II) complexes
with PEG-b-PAA [106].
Apart from surfactants and polymers, biomacromolecules such
as nucleotides and proteins can also co-assemble with organoplat-
inum(II) complexes [109,110]. Recently, De Cola, Cornelissen and
co-workers have reported a fascinating system comprising plat-
inum(II) amphiphiles (28 or 29) and the coating protein (CP) of
cowpea chlorotic mottle virus (Fig. 15) [110]. The latter one is pos-
itively charged, which tends to complex with the negatively
charged platinum(II) amphiphiles 28–29 via electrostatic interac-
tions at the neutral buffer solution. Interestingly, by tuning the side
chains on 28–29, morphology of the final co-assembled structures
can be modulated. In detail, co-assembly between 28 and CP leads
to the presence of spherical particles, with the diameters of
approximately 18 nm (Fig. 15). It is rationalized that protein–
protein interactions dominates for the 28/CP co-assembly process,
since the aggregates derived from 28 itself are evidently smaller
than the inner cavity of icoshahedral protein cage (ca. 21 nm). In
stark contrast, co-assembly between 29 and CP generates rod-
like nanostructures (length: 100–500 nm, thickness: 18 nm,
Fig. 15). It lies in the formation of long (>50 nm) and thin
(~6 nm) rods for the 29 self-aggregated structure. Accordingly,
the electrostatic interactions between 29 and CP force the forma-
tion of non-icosahedron morphology.
Besides, hybrid organic–inorganic system can be attained,
by employing organoplatinum complexes as one of the
14 Y. Han et al. / Coordination Chemistry Reviews 414 (2020) 213300
Fig. 15. Graphic representation for supramolecular co-assembly systems between coating protein of cowpea chlorotic mottle virus and platinum(II) amphiphiles 28 or 29.
Reproduced with permission of 2018 American Chemical Society from [110].
Fig. 16. Graphic representation for the end-to-end and side-by-side assembly of
gold nanorods via the assistance of platinum(II) complexes 30 and 31, respectively.
Reproduced with permission of 2016 American Chemical Society from [111], and
2018 Wiley-VCH Verlag GmbH from ref. [112].
co-assembling building blocks. Yam and co-workers have designed
a positively-charged Pt(terpy) complex 30, consisting of a thioac-
etate unit on the periphery (Fig. 16) [111]. Upon adding pyrro-
lidine, the in situ deprotected form of 30 would preferentially
attach to the active ends of the gold nanorods (GNRs). As a conse-
quence, GNRs aggregate into chain-like structures via end-to-end
assembly (Fig. 16), which is mediated by non-covalent Pt(II)–Pt
(II) metal–metal and p–p stacking interactions provided by the
Pt(terpy) units. The instinct factor for end-to-end assembly lies
in the stabilization layer of GNRs, which is composed of the inter-
digitated bilayer of cationic cetrimonium bromide (CTAB). Since
CTAB displays a better binding affinity towards the {1 0 0} and
{1 1 0} side facets than the {1 1 1} end facets, the GNRs sides have
a better passivation with CTAB. As a consequence, 30 prefers to
attach on the ends of GNRs. In an extensive study, side-by-side
assembly of GNRs have also been realized by the same group, by
rational designing of negatively-charged Pt(terpy) complex 31
(Fig. 16) [112]. The sulfonate moieties on 31 feature high cation-
binding affinity, which preferentially bind to the ammonium head
groups of CTAB along the sides of the GNRs. Accordingly, it brings
the neighboring GNRs together in a side-by-side manner, which
can be visualized by electron microscopy (Fig. 16). The study
demonstrates that well-ordered inorganic–organic hybrid assem-
blies can be achieved via the elaborate choice of organoplatinum
(II) building blocks.
3. Functionality of organoplatinum(II)-based supramolecular
nanostructures
3.1. Sensing materials
During supramolecular assembly/disassembly of organoplat-
inum(II) complexes, the low-energy MMLCT transition signals
emerge and disappear in a reversible manner. Taking advantage
of this property, together with the aforementioned
‘‘polyelectrolyte-induced assembly” concept [105], Yam and
coworkers have exploited the applications of organoplatinum(II)-
based assemblies in chemo-sensing field. For example, they con-
struct a hybrid co-assembling system {poly(phenylene ethynylene
sulfonate) (abbreviated as PPE-SO
3 ) and [Pt(terpy){C„CAC6H4-
ACH2N(CH3)3}](OTf)2)}, with the involvement of Förster resonance
energy transfer (FRET) character [113]. When human serum albu-
min (HSA) is added, it binds strongly with PPE-SO
3 , and thereby
leads to the disassembly between Pt(terpy) and the anionic poly-
mer. Accordingly, label-free detection of HSA is realized in a sensi-
tive and selective manner, by monitoring the ratiometric spectral
changes between MMLCT and MLCT/LLCT signals. The label-free
sensing strategy has also been applied by the same group to the
specific detection of glucose [114], lysozyme [115], thrombin,
 Y. Han et al. / Coordination Chemistry Reviews 414 (2020) 213300
Fig. 17. Graphic representation for visual chiral recognition of chiral binap through
enantioselective metallogel collapsing. Reproduced with permission of 2011 Wiley-
VCH Verlag GmbH from ref. [119].
human telomere DNA [116], protamine [117], heparin [118], and
etc. Readers could refer to a nice review for more detailed informa-
tion [20].
In addition, an interesting visual chiral recognition system has
been reported by Tu and co-workers [119]. Briefly, 32 (Fig. 17) is
designed with a chloro alkynylplatinum(II) core. The compound
is capable of forming supramolecular organogels, by entrapping
various aprotic solvents such as chloroform, dichloroethane,
dimethylacetamide, and benzonitrile. The chloride unit on 32
undergoes ligand exchange with the bulky phosphine ligands. It
gives rise the huge steric hindrance, and thereby inducing the
Fig. 18. (a) Structures of 33 and 34, together with graphic representation of aggregation-induced electrochemiluminescence behavior of 34. (b) Circularly polarized
luminescent behaviours of organoplatinum(II)-based enantiomers (+)-35 and (
)-35. Reproduced with permission of 2017 American Chemical Society from [122], and 2015
American Chemical Society from [124].
15
collapse of organogels. Remarkably, chiral discrimination of (R)-
and (S)-2,20 -bis(diphenylphosphino)-1,10 -binaphthyl (abbreviated
as (R)- and (S)-binap, respectively) enantiomers is achieved,
through a visually enantio-controlled breakup of the supramolecu-
lar gels (Fig. 17). The chiral recognition behaviors are strongly cor-
related with metal-coordination capability of the chiral phosphine
ligands. (R)-Binap phosphine coordinates efficiently to the plat-
inum center (Fig. 17), leading to the breakup of intermolecular Pt
(II)–Pt(II) metal–metal and p–p stacking interactions. On the con-
trary, ligand exchange hardly occurs for (S)-binap phosphine ligand
(Fig. 17), because of its chirality mismatching with the chiral
supramolecular gels.
3.2. Emitting materials
Upon supramolecular assembly of organoplatinum(II) com-
plexes, it decreases non-radiation decay rate and thereby enhances
the emission intensity. Additionally, spin-coating and ink-jet print-
ing techniques can be employed to fabricate ordered films. It thus
avoids the expensive vacuum deposition technique encountered
for small molecules, and thereby reduces the cost for manufactur-
ing [120]. Based on these considerations, organoplatinum(II)-based
nanostructures display promising prospects for emitting applica-
tions. De Cola and coworkers have reported a neutral organoplat-
inum(II) compound 33 (Fig. 18a), which forms nanofibers and
gels in hexane with aggregation-induced green emission character
[PLQY (photoluminescence quantum yield) = 90% at the gelation
state, and 87% in thin film] [121]. When 10 wt% of 33 is doped in
the emissive layer, the maximum current efficiency (gc,max) is
15.6 cd A
1 (4.5 Lm W
1) at a brightness of 203 cd m
2. The max-
imum brightness of OLEDs is determined to be 11360 cd m
2.
Hence, the ‘‘turn-on” luminescent character of organoplatinum
(II)-based nanostructures is attractive for OLEDs applications.
16 Y. Han et al. / Coordination Chemistry Reviews 414 (2020) 213300
Later on, the same group has also investigated aggregation-
induced electrochemiluminescence (AIECL) behaviors of
organoplatinum(II) complexes 34 (Fig. 18a) on the surface of elec-
trode [122]. Although molecularly dissolved state dominates for 34
at the ambient state, gentle grinding of its powder facilitates the
conversion to the aggregated structure. It is accompanied by the
emission color change from blue to orange. Remarkably, the aggre-
gated sample of 34 shows 20-fold enhancement in ECL emission
intensity, when comparing to the blue-emissive sample prior to
the grinding process (Fig. 18a). Unambiguously, supramolecular
assembly is of particularly importance toward emissive materials
with the high ECL intensity.
Circularly polarized luminescent (CPL) materials have also
aroused significant interests in recent years, because of their
potential applications in 3D display and optical identification sen-
sor [123]. The prerequisite of CPL emitters requires the embed-
ment of emission and chirality characters in a concurrent
manner. In this regard, You’s group has reported the
organoplatinum(II)-based enantiomers (+)-35 and (
)-35
(Fig. 18b), featuring the asymmetric pinene on the tridentate
cyclometalated ligand [124]. The chiral pinene units benefit for
the formation of helical supramolecular aggregates in water.
Accordingly, CPL signals emerge for both enantiomers with the
opposite helicity. The glum values around the maximum emission
wavelength are calculated to be 0.0012 and –0.0018 for (+)-35
and (
)-35 at 295 K, respectively (Fig. 18b). Organoplatinum(II)-
based CPL materials are also developed by Haino and coworkers
[125,126]. When tris(phenylisoxazole)-linked point-chiral alkyl
chains are attached to the Pt(II) phenylbipyridine core, it shows
aggregation-induced emission enhancement character. Accord-
ingly, the resulting assemblies feature a pronounced glum value
(~0.01), despite the fact that neither CD nor CPL signal is observed
at the monomeric state.
As discussed above, our research group has successfully assem-
bling platinum(II) acetylides 2b (Fig. 2b) into fluorescent
supramolecular polymers via the cooperative mechanism [38].
Fig. 19. (a) Crystalline packing structure of 36 and the output characteristics of FET device fabricated from 36 (VDS: drain–source voltage, VG: gate voltage). (b) Crystal packing
structure and p-channel characteristic of the 37 micro-crystal. Reproduced with permission from 2009 Wiley-VCH Verlag GmbH from ref. [128], and 2011 Royal Society of
Chemistry from ref. [129].
The resulting high-molecular-weight supramolecular polymers
are capable of forming electrospun microfibers with uniform
geometry and smooth surface. It enables light propagation with
high anitrosopy and extremely low scattering loss (0.008 dB lm
1).
Hence, the study provides a novel avenue toward high-
performance optical waveguiding materials, by combining
bottom-up supramolecular polymerization and top-down electro-
spinning techniques in an elaborate manner. Giving that chirality
signals emerges at the self-assembled state, it is expected that
flourescent supramolecular polymers derived from 2b also possess
CPL signal, which is now underway in our labotorary.
3.3. Semi-conductive materials
Organic semiconductors have aroused tremendous interest
because of their potential application in field-effect transistors
(FET) and photovoltaic cells [127]. Supramolecular assembly of
p-conjugated molecules represent a plausible route to provide bulk
semi-conducting materials. In this context, Che and coworkers
have reported a series of alkynylplatinum(II) complexes with the
tridentate 1,5-bis(20 -pyridine)benzene ligands [128]. For one of
the synthetic compound 36 (Fig. 19a), it is capable of assembling
into quasi-two-dimensional nanosheets. Depending on X-ray mea-
surement, infinite Pt–Pt chains exist with a short intermetal con-
tact of 3.383 Å (Fig. 19a). Neighboring molecules are arranged in
a staggered fashion with a torsion angle of 49.4° around the Pt–
Pt axis. The hole-transporting properties are further studied for
the drop-casting nanosheets of 36. Upon switching on and off the
white light (intensity: 40 mW cm
2) for every 5 s, a transient chan-
nel current is detected when drain-source voltage (VDS) and gate
voltage (VG) are ±40 V. More intriguingly, the field-effect transistor
device shows an increase in the density of forward and backward
current after photoexcitation (Fig. 19a).
Notably, the charge-transporting properties can be optimized
via the rational choice of ligand unit on organoplatinum(II) com-
plexes. For another compound 37 (Fig. 19b) designed by the same
 Y. Han et al. / Coordination Chemistry Reviews 414 (2020) 213300
Fig. 20. Supramolecular self-assembly and gelation behaviours of 38, together with
time-dependent HeLa cell survival upon treating with the hydrogel or cisplatin
under the neutral or acidic incubation conditions. Reproduced with permission of
2015 Royal Society of Chemistry from [131].
group [129], two pyrazolyl units are incorporated into the main
ligand, which enable the formation of intermolecular hydrogen
bonds. In the crystal structure (Fig. 19b), such non-covalent forces
are harmonized with extended p–p and Pt(II)–Pt(II) metal–metal
interactions to align the planar cations into a long-range ordered
quasi-1-D columnar structure. The co-facial configuration of 37
enhances the charge-hopping process inside the single crystal.
Fig. 21. (a) Hexagonal honeycomb-like porous networks assembled from 39, together with the adsorption performance toward the diverse cations and anions. (b) Hybrid
composites ZJU-28/40 and ZJU-28/41, together with the TON values for photo-catalyzed dehydrogenation reaction of 1-phenylethanol. Reproduced with permission of 2019
American Chemistry Society from [132], and 2018 Royal Society of Chemistry from [133].
17
Accordingly, the electron mobility (le) value reaches to the
remarkable value of 20 cm2 V
1 s
1 for FET device measurements
(Fig. 19b).
3.4. Biomedical materials
As widely documented, cisplatin and carboplatin display high
chemotherapeutic efficiency toward cancer cells. It stimulates the
development of novel organoplatinum(II)-based anti-tumor drugs.
Che’s group has reported some promising candidates in this field
[130,131]. For example, supramolecular hydrogel derived from
38 (Fig. 20) shows sustained and pH-dependent releasing behav-
iors. Under the acidic conditions, the survival percentage for HeLa
cells is determined to be ca. 30% after incubation for 6 h (Fig. 20).
However, it takes 72 h of incubation treatment to reach 29% cell
survival under neutralized condition (Fig. 20). Accordingly, the
acidic condition is favorable for the enhanced cytotoxicity, which
is associated with pH-dependent assembling capability of 38 in
water. In detail, 38 is prone to accumulate in the acidic lysosomes
of HeLa cells, leading to the increase in lysosomal membrane
permeability. With the further combination of strong emission
and chemotherapeutic characters, organoplatinum(II)-based
supramolecular nanostructures have also demonstrated promising
prospects in the theranostics fields.
3.5. Other potential applications
Organoplatinum(II)-based supramolecular nanostructures can
be also endowed with other functionalities. For example, Yam
and co-workers have designed a homotritopic monomer 39
(Fig. 21a), which tends to form hexagonal honeycomb-like porous
structure [132]. Intriguingly, the resulting polycationic
18 Y. Han et al. / Coordination Chemistry Reviews 414 (2020) 213300
two-dimensional supramolecular polymers selectivity recognize
anionic platinum(II) complexes such as PtCl2
4 from the guest mix-
ture. The high affinity toward PtCl2
4 is correlated with the strong
Pt–Pt interactions. The supramolecular polymeric material can be
processed into composite membrane on the surface of polycarbon-
ate filter support, which also exhibits encapsulation preference for
the anionic platinum(II) complexes (the adsorption capacity:
33 mg g
1, Fig. 21a).
Besides, Che and co-workers have reported an interesting
hybrid co-assembly system for photo-catalytic application
(Fig. 21b) [133]. For metal organic frameworks (ZJU-28), their
one-dimensional channels provide ‘‘solid solution” environments.
As a result, it facilitates to encapsulate 40 and 41 (Fig. 21b) in
the supramolecular assembled form. The hybrid composites ZJU-
28/40 and ZJU-28/41 show good performance for the photo-
catalyzed C–H dehydrogenation reactions. Upon photo-irradiation
at room temperature, 1-phenylenthanol transforms into acetophe-
none with high turn-over numbers [TONs: 363 for ZJU-28/40
(1.36% loading); 210 for ZJU-28/40 (1.50% loading); 252 for ZJU-
28/41 (1.32% loading); 160 for ZJU-28/41 (2.41% loading)]. Note-
worthily, trace amount or even no products can be detected for
either organoplatinum(II) photocatalysts or ZJU-28 at the individ-
ual form. It is rationalized that 3MMLCT excited states derived from
the 40 (or 41) self-aggregation process is crucial for the photo-
catalytic reactions, considering that the diradical features of 3-
MMLCT excited states facilitate to hydrogen atom extraction from
C–H bonds.
4. Conclusion
In conclusion, the state-of-art progress of long-range ordered
organoplatinum(II)-based nanostructures has been summarized.
Square-planar organoplatinum(II) complexes are regarded as ideal
supramolecular building blocks, which facilitate to incorporate a
variety of non-covalent forces such as p–p stacking, metal–metal,
and hydrogen bonding interactions. Delicate manipulation of these
non-covalent bonds give rise to diverse assembling modes. With
the deeper understanding of the assembling mechanism and path-
way, it is capable of constructing supramolecular nanostructures
with the tailored properties. By combining the advantageous from
organoplatinum(II) complexes (such as fascinating photo-physical
and therapeutic properties) and long-range ordered nanostruc-
tures (such as excellent solution processability and the collective
signal amplification), the resulting systems have displayed promis-
ing prospects in sensing, optoelectronics, biomedical, and environ-
mental fields.
Despite all of these achievements, there are still some issues to
be solved from the perspective of supramolecular chemistry.
Firstly, monodispersity is in keen pursuit for long-range ordered
organoplatinum(II) assemblies, since polydisperse nanostructures
are obtained for the vast majority of the reported examples. In this
respect, ‘‘seeded growth approach” proposed by Manners repre-
sents a promising strategy to tackle the problem. To attain this
objective, it requires the adoption of nucleation–elongation coop-
erative mechanism for organoplatinum(II)-based assemblies,
meanwhile the supramolecular assembly process should be kinet-
ically trapped to retard spontaneous nucleation. Accordingly,
incorporation of monomeric species takes place only from the
seed’s ends to provide defined aggregation length, the phenomena
of which are similar to that of covalent living polymerization.
Although Manners and co-workers have demonstrated one fasci-
nating example in this field [94], adaptability of the strategy to
other organoplatinum(II)-based assembled systems should be
examined.
Secondly, in addition to mono-component supramolecular sys-
tem, more and more attentions should be paid to the co-assembled
organoplatinum(II)-based systems. A variety of possible orienta-
tion modes can be generated, including segregated stacks, block
co-assembly, randomly mixing co-assembly, and alternately mix-
ing co-assembly. It is mainly ascribed to the inter- and intra-
chain exchange of monomers, because of the kinetic lability of
non-covalent forces involved in the co-assembly processes. In this
regard, domain control is a challenging task for supramolecular
chemists in this field. Although we and other research group have
successfully directed the formation of strictly alternate co-
assemblies [101–103], other types of precise orientation modes
such as multi-block copolymers have yet to be explored.
Thirdly, the current reported organoplatinum(II)-based
supramolecular assemblies are mainly in the ‘‘static” equilibrium
state. In comparison, out-of-equilibrium supramolecular systems,
denoting the supply and consumption of energy during the assem-
bling processes, are seldom exploited. The out-of-equilibrium dis-
sipative state could not reach to the global minima, according to
the energy landscapes of supramolecular systems. Nevertheless,
it is highly mimicking of natural assembled systems, facilitating
to interconvert rapidly and reversibly between various
supramolecular structures. Overall, in-depth understanding of
supramolecular assembling behaviors would benefit for the excit-
ing new applications of such organoplatinum(II)-based systems in
the future.
Conflict of interest
The authors declare no conflict of interest.
Acknowledgments
This work is supported by the National Natural Science Founda-
tion of China (Grants 21922110, 21871245, and 21674106), the
Fundamental Research Funds for the Central Universities (Grant
WK3450000004), the CAS Youth Innovation Promotion Association
(Grant 2015365).
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.ccr.2020.213300.
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