Terpyridine-based metallo-organic cages and supramolecular gelation by coordination-driven self-assembly and host-guest interaction

Article abstract of DOI:10.1039/c8dt01044g

Host-guest complexation based on terpyridine (tpy) three-dimensional (3D) metallo-cages has received less attention due to the complicated structure and solubility issues. Herein, a three-armed metallo-organic ligand (L) was synthesized via three 120°-ben

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Terpyridine-based Metallo-organic Cage and Supramolecular
Gelation by Coordination-driven Self-assembly and Host–guest
Interaction
Received 00th January 20xx,
Accepted 00th January 20xx
Die Liu,a‡ Haisheng Liu,a‡ Bo Song,b Mingzhao Chen,a Jian Huang,a Jun Wang,a Xiaoyu Yang,a Wei
DOI: 10.1039/x0xx00000x
Sun,a* Xiaopeng Lib* and Pingshan Wanga*
www.rsc.org/
Host-guest complexation based on terpyridine (tpy) three-dimensional (3D) metallo-cages received less attention due to
the complicated structure and solubility issue. Herein, a three-armed metallo-organic ligand (L) was synthesized via three
120°-bent bis-tpy groups into rigid tetrakis-tpy core, which possesses one benzo-21-crown-7 (B21C7) for further host-guest
interaction. The metallo-organic cages [M3L2] with molecular weight up to 13,000 Da and a giant cavity was prepared in
near-quantitative yield by self-assembly of L with metal ions, such as Zn2+ and Fe2+. The 3D metallo-supramolecules were
characterized and supported by NMR, DOSY, ESI-MS and TEM. Hosts [M3L2] were threaded through a difunctional
alkylammonium salt by host–guest interactions to polymerize, and subsequently generate the novel metallo-gels between
[Zn3L2] and bis-ammonium salt (N2).
Introduction
To construct more elaborate and complex metallo-supra-
architectures and to further realize the functionality, the step-
wise assembly was frequently used as an alternative strategy,
when one-pot self-assembly was unable to construct complex
architectures under thermodynamic control.10 More recently,
using the step-wise strategy on stable tpy-Ru2+-tpy metallo-
organic ligand (MOL) to assemble complicated and yet elegant
metallo-supramolecule has been demonstrated to create the
2D or 3D architectures with large molecular weights.11 This
strategy thoroughly avoids the self-sorting of polyterpyridinyl
subcomponents and provides possibility for the self-assembly
of desired multicomponent 2D or 3D supra-structures.
Furthermore, the functional moieties anchored on terpyridinyl
precursor could be conveniently introduced into
supramolecule via stable tpy-Ru-tpy complexity.
Supramolecular self-assembly is a key process in life systems
to create abundant well-defined abiological architectures with
special functionalities, such as DNA double helical structure1
and viral capsid2-4. In the journey of mimicking biological
systems, a variety of non-covalent interactions has been
exploited to construct the functionalized supramolecular self-
assemblies, such as van der Waals, π−π stacking, hydrogen
bonding, metal−ligand interactions, etc.5-7 Among these
interactions, coordination-driven terpyridinyl self-assembly of
discrete supramolecular architectures with predesigned, well-
defined sizes and shapes has drawn extensive attentions due
to their highly directional and predictable feature. Up to date,
a series of terpyridine supramolecules have been successfully
prepared, from two-dimensional (2D) macrocycles,4 spoked
wheel5 and fractals6 to three dimensional (3D) cages7 and
polyhedrons.8 However, the functionalization of this kind of
supramolecular architectures was rare.9
Crown ether host/guest reciprocal interactions, which
exhibited better selectivity, higher efficiency and peculiar
reversibility, have been widely employed in the construction of
supramolecular materials.12 Therefore, taking advantage of the
coordination-driven self-assembly and host-guest interactions
between crown ether and ammonium substrates to construct
a supramolecular system is feasible and meaningful.13 Herein,
using the step-wise strategy and tetrakis(4-(4-(4'-[2,2':6',2'']
terpyridyl) phenyl) phenyl)methane as the rigid core, the
a.Department of Organic and Polymer Chemistry, College of Chemistry and
Chemical Engineering, Central South University, Changsha, Hunan-410083, China.
E-mail: chemwps@csu.edu.cn
b.Department of Chemistry, University of South Florida, Tampa, FL 33620, USA. E-
mail: xiaopengli1@usf.edu
metallo-organic ligand
L with three uncomplexed terpyridinyl
† Electronic Supplementary Information (ESI) available: Full experimental details,
the 1H NMR, 13C NMR, COSY, ROESY, and UV spectra of the new compounds, ESI-
MS spectra of related compounds. See DOI: 10.1039/x0xx00000x
‡ These authors contributed equally to this work.
arms in nearly parallel juxtaposition were synthesized by
sequentially incorporating one benzo-21-crown-7 (B21C7)
functionalized terpyridine and three 120°-bent bis-terpyridine
via the terpyridine-Ru2+-terpyridine (<tpy-Ru2+-tpy>)
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Scheme 1 Schematic illustration of preparing dimetallo-organic supramolecular cages
[M3L2] (M =Zn2+ or Fe2+) and host–guest interactions with symmetrical difunctional
alkylammonium salt N2.
coordination linkages. Subsequently, two crown ethers
contained terpyridinyl metallo-organic cages [Zn3L2] and [Fe3L2
]
were readily prepared via self-assembly of ligand L with metal
ion (Zn2+ or Fe2+). The host-guest interaction between crown
ether-cages (host) and alkyl-ammonium salt was confirmed,
and the thermodynamically controlled metallo-gel was
prepared via polymerization by using bis-ammonium salt N2
Scheme 2 Synthesis of Ligands L: (i,ii) N-ethylmorpholine, CHCl3/CH3OH, refluxed; (iii)
(scheme 1).
Pd(PPh3)4, K2CO3, CH3CN, refluxed.
stoichiometric ratio of 2:3 in MeCN, followed by adding excess
NH4PF6 solution to afford a red precipitate, which was washed
Results and discussion
Tetrakisterpyridine compound
4 (scheme 2) was prepared
with pure water and dried in vacuo. Although the cages [Zn3L2
]
by Suzuki coupling from tetrakis(4-bromophenyl)methane
and [Fe3L2] contained 11 metal ions and 22 tpy moieties, both
complexes were soluble in MeCN due to the multiple methoxy
and crown ether moieties. [Zn3L2] and [Fe3L2] were determined
according to previous report.14 The trifurcated free-terpyridine
5
was obtained as a red solid by stirring Ru3+ monoadduct
3
1
with excess compound
4 in CH3OH/CHCl3 (v/v 2:1) in the
by H NMR, COSY, NOESY, DOSY, ESI-MS spectroscopies along
presence of N-ethylmorpholine for 24 h and purified by the
flash column chromatography (Al2O3, CHCl3/MeOH). Similarly,
with TEM. However, attempt to grow X-ray quality single
crystals of [Zn3L2] and [Fe3L2] was unsuccessful possibly due to
its relatively flexible structure.8c
the key precursor Br-substituted complex
synthesized from
by treatment with 3.6 eq. Ru3+ monoadduct
. H NMR of complex displayed three sharp singlets of
methoxy group at 4.95, 3.87 and 3.72ppm with a 1:1:1
integration ratio (Figs. S16-S18, ESI ), agreeing well with the
expected structure. The key metallo-organic ligand was
prepared via a final Suzuki coupling with and {4'-(4-
8 was readily
5
1
1H NMR of complexes [Zn3L2] and [Fe3L2] (Figure
1) showed
7
8
comparatively distinct patterns for the expected peaks, but the
notable attributes were complicated caused by the multiple
complexation environment from different tpy moieties. The
characteristic signals were observed for the tpyH3’,5’ protons
(at 9.10 ppm for [Zn3L2] and 9.27 ppm for [Fe3L2] ) from tpy
part-E, which showed significantly downfield-shift compared
†
L
8
boronatophenyl)[2,2':6',2'']} terpyridine and further purified
by flash column chromatography (Al2O3) eluting with
CH2Cl2/CH3OH. The methoxyl groups at the corner of three
120°-bent bis-terpyridine have been introduced for
significantly enhancing the solubility.
with L at 8.77 ppm.
Also, the tpyH6,6’’protons moved significantly upfield owing
1H NMR of ligand
L was discernible compared to its
1
to electron shielding effects after coordination. The broad H
precursor
8
. A new singlet for tpyH3’,5’ signals at 8.77ppm
NMR signals could be rationalized by the large cage-like
complexes, which have slow tumbling motion on the NMR
time scale.15 Although there were multiple sets of protons of
tpy and phenyl units for the results of substantial overlap of
the multiple tpy moieties, the corresponding peaks of five
different tpy units with the expected integration ratio could
been successfully assigned based on the analysis of 2D COSY
and 2D ROESY NMR spectra.
showed an up-shift compared with coordinated tpyH3’,5’ peaks
in <tpy-RuII-tpy>, suggesting three free terpyridine moieties
were successfully incorporated. Moreover, the high-resolution
- 5+
ESI-MS confirmed the structure
L as m/z: 1065.09 [M-5PF6 ]
- 6+
(calcd. m/z = 1065.06) and 863.42 [M-6PF6 ] (calcd. m/z =
863.39). The measured isotopic patterns of were consistent
with the calculated peaks (Fig. S3, ESI ).
Metallo-organic cages [Zn3L2] and [Fe3L2] were prepared
(scheme ) by mixing and Zn(NO3)2 (or FeCl2) in a precise
L
†
3
L
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Scheme 3 Metallo-organic ligand L and self-assembly of bimetallo-organic cages [M3L2] (M =Zn2+ or Fe2+).
Fig. 1 Partial 1H NMR spectra (500 MHz) of metallo-organic ligand L, supramolecular cage [Zn3L2] and [Fe3L2] in CD3CN.
Diffusion-ordered NMR spectroscopies (DOSY) of ligand L(Fig. structures possessed similar size and connectivity. Further, the
S22, ESI†), complexes [Zn3L2] and [Fe3L2 were shown Figure 2 for dynamic diameter was calculated to be 7.8 nm for Fe3L2] and 8.4
Fe3L2 and Fig.S26 for [Zn3L2]. In DOSY, the observation of a nm for [Zn3L2] which were approximately equal to twice of 5.1 nm
distinct band of Fe3L2 showed a narrow band at log D= -9.85, for L, demonstrating the forming of cage-like structure.
indicating the formation of a single discrete product. Similarly, the
log D = -9.82 of [Zn3L2] was approximately close to that of Fe3L2
The near diffusion coefficient of 1.51 × 10-10 m2 s-1 for
Fe3L2 and characterized by ESI-MS to endorse the proposed structures
1.41 × 10-10 m2 s-1 for [Zn3L2] demonstrated that both cage-like with molecular weights of 13166.8 Da and 13137.8 Da,
]
[
[
]
[
]
[
]
.
Metallo-cages [Zn3 L2] and [Fe3L2] were further
[
]
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length of 7.5 nm and width of 4.2nm respectively, in close
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DOI: 10.1039/C8DT01044G
agreement with values obtained from molecular modelling (Fig.
4
,right). And corresponding TEM images of [Zn3L2] was shown
in Fig. S31. Further, the average diameter of cages [Zn3L2] and
Fe3L2] were determined to be 7.5 nm by the DLS experiment,
which supporting the forming of cages (Fig. (b) and Fig. S32).
[
4
To evaluate the feasibility of complicated host/guest
threaded structures, [Zn3L] and [Fe3L2] were dissolved in
CH3CN/CHCl3 (1:2) and then ammonium salt as guest was
1
added with same solvent proportion. Partial proton H NMR
experiments furnished insights into the complexations of
Zn3L2] or [Fe3L2] with ammonium salt guests (N1), respectively
Fig. 2 DOSY spectrum (500 MHz) of supramolecular cage [Fe3L2] in CD3CN.
[
1
(shown in Fig.
5
(b), Fig. S36, ESI
†
). Comparisons of H NMR
spectrum of [Zn3L2], ammonium salt and their mixture
revealed the apparent chemical shift changes. As shown in Fig.
5
(b), the partial crown ether 1H NMR spectrum of the mixtures
was complicated and divided into five sets which were
corresponding to the complex species. Due to the 3D hosts
possessing the molecular weights of over 13 kDa, crown ether
protons all shifted slightly. Downfield chemical shift changes
were observed for ethylenoxy protons of Ha,b, Hc,d, He,f, Hi,
while Hg,h shifted upfield after complexation, which was in
accordance with the well-known B21C7/alkylammonium
complexation motif.17
The supramolecular metallo-gel was prepared via
polymerization of [Zn3L2] and bis-ammonium salt (N2) (Fig.
6
a).
[
Zn3L2] in mixed CH3CN/H2O solution at ambient temperature.
Supramolecular network and gelation were observed with the
gradual increase of viscosity in results of linkage between
B21C7 and ammonium salt moieties. When [Zn3L2] (host)
interacted with N2 (guest), there were some structural forms in
this gel, such as intertwined dimers, oligomers and polymers.18
According to metallo-organic gel, herein, we could deduce that
Fig. 3 ESI-MS spectrum of cage [Fe3L2].
respectively. In ESI-MS, the charge states of integrated
assemblies were exhibited. A series of dominant peaks of
[
Fe3L2] were detected corresponding to charge states of 8+ to
20+ generated by the loss numbers of PF6¯ anions and
corresponding experimental isotope patterns were in well
agreement with the calculated patterns (Fig. 3 and Fig. S7, ESI
the polymers played a dominant role. As shown in Figs. 6(b,c),
S40 and S41, the fabrication of gel was examined by TEM,
scanning electron microscopy (SEM) and atomic force
microscope (AFM). Although the SEM and AFM images did not
indicate the obvious fibrous morphology, the TEM image
exhibited an entangled extended and interconnected fibrous
network indicative of the polymeric network formation.
†
). Similarly, [Zn3L2] was observed a series of peaks from 7+ to
16+ (Fig. S4, ESI
agreement with their calculated theoretical distributions (Fig.
S5, ESI ). There existed the bumpy ground line in the mass
†) and were isotopically resolved in excellent
†
spectrum may due to the encapsulation of solvent or salt
molecules inside the cage.8(c),16
Conclusions
In summary, we have demonstrated a highly efficient
approach of constructing host-guest complexations of tpy-
based three-dimensional (3D) dinuclear metallo-organic cages.
By careful design of 120°-bent tpy groups into rigid core,
thenovel bipyramidal structures functionalized with two
crown-ether groups were successfully synthesized. Multiple
NMR (1H NMR, 2D COSY, NOESY and DOSY NMR) analysis
supported the formation of discrete resultant products. ESI-MS,
TEM and DLS provided the further evidences of precise
molecular structures and exact molecular weights, molecular
Fig.
4 (a)TEM image of supramolecular cage [Fe3L2] and representative energy-
minimized structure from molecular modeling. (b) the dynamic light scattering (DLS)
graph of cage [Zn3L2].
The size and shape of [Fe3L2] were imaged by transmission
electron microscopy (TEM) (Fig.
4). The TEM images
manifested highly dispersed [Fe3L2] with an approximate
4 | J. Name., 2012, 00, 1-3
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This research was supported by the National Natural Science
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Foundation of China (21274165 for DPOWI: 1,0.1501396/3C480D0T9010a4n4Gd
51374247 for WS), the Distinguished Professor Research Fund
and the Fundamental Research Funds from Central South
University (2013zzts014), NSF (CHE-1506722 XL. The authors
gratefully acknowledge the NMR spectroscopy measurements
from the Modern Analysis and Testing Center of CSU.
Notes and references
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Dalton Transactions
View Article Online
DOI: 10.1039/C8DT01044G
Terpyridine-based Metallo-Organic Cage and Its Supramolecular Gelation by
Coordination-driven Self-Assembly and Host–Guest Interactions
Die Liu, Haisheng Liu, Bo Song, Mingzhao Chen, Jian Huang, Jun Wang, Xiaoyu
Yang, Wei Sun, Xiaopeng Li and Pingshan Wang
Publication Date (Web): 2018 (Communication)
DOI: xxx
Dalton Transactions, 2018.
Dimetallo-cages engendered through a predesigned metallo-orangic ligand and Fe2+
(or Zn2+). Cage connected with Dialkylammonium salt via host–guest interaction
caused the thermodynamic polymer metallo-gel.