Guest-Reaction Driven Cage to Conjoined Twin-Cage Mitosis-Like Host Transformation

Article abstract of DOI:10.1002/anie.202011474

We report here a guest-reaction-induced mitosis-like host transformation from a known Pd₄L₂ cage 1 to a conjoined Pd₆L₃ twin-cage 2 featuring two separate cavities. The encapsulation of 1-hydroxymethyl-2-naphthol (G1), a known ortho-quinone methide (o-QMs) precursor, within the hydrophobic cavity of cage 1 is found crucial to realize the cage to twin-cage conversion. Confined G1 molecules within the nanocavity undergo self-coupling dimerization reaction to form 2,2′-dihydroxy-1,1′-dinaphthylmethane (G2) which then triggers the cage to twin-cage mitosis. The same conversion also proceeds, in a much faster rate, via the direct templation of G2, confirming the induced-fit transformation mechanism. The structure of the (G2)₂?2 host–guest complex has been established by X-ray crystallographic study, where cis- to trans- conformational switch on one bridging ligand is revealed.

Full text of DOI:10.1002/anie.202011474

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Accepted Article
Title: Guest-Reaction Driven Cage to Conjoined Twin-Cage Mitosis-
Like Host Transformation
Authors: Pei-Ming Cheng, Li-Xuan Cai, Shao-Chuan Li, Shao-Jun Hu,
Dan-Ni Yan, Li-Peng Zhou, and Qing-Fu Sun
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To be cited as: Angew. Chem. Int. Ed. 10.1002/anie.202011474
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Guest-Reaction Driven Cage to Conjoined Twin-Cage Mitosis-Like
Host Transformation
Pei-Ming Cheng, [a][b] Li-Xuan Cai, [a] Shao-Chuan Li, [a][c] Shao-Jun Hu, [a][c] Dan-Ni Yan, [a][c] Li-Peng
[
a]
[a][c]
Zhou , and Qing-Fu Sun*
Dedication
[a]
P.-M. Cheng, Dr. L.-X. Cai, S.-C. Li, S.-J. Hu, D.-N. Yan, Dr. L.-P. Zhou, Prof. Q.-F. Sun
State Key Laboratory of Structural Chemistry
Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, PR China
E-mail: qfsun@fjirsm.ac.cn
[
b]
c]
P.-M. Cheng
College of Chemistry and Material Science
Fujian Normal University, Fuzhou 350007, PR China
S.-C. Li, S.-J. Hu, D.-N. Yan, Prof. Q.-F. Sun
[
University of Chinese Academy of Sciences, Beijing 100049, PR China
Supporting information for this article is given via a link at the end of the document.
Abstract: We report here a guest-reaction induced mitosis-like host
transformation from a known Pd cage 1 to a conjoined Pd twin-
hetero Diels-Alder or nucleophilic additions.12 As such, o-QMs
precursors can be used as ideal cross-linker agents to DNAs,
proteins and enzymes.13 It is well-known that container-
molecules have great potential in taming highly reactive
chemicals through supramolecular encapsulation and isolation.14
4
L
2
6 3
L
cage 2 featuring two separate cavities. The encapsulation of 1-
hydroxymethyl-2-naphthol (G1), a known ortho-quinone methide (o-
QMs) precursor, within the hydrophobic cavity of cage 1 is found
crucial to realize the cage to twin-cage conversion. Confined G1
molecules within the nanocavity undergo self-coupling dimerization
reaction to form 2,2'-dihydroxy-1,1'-dinaphthylmethane (G2) which
then triggers the cage to twin-cage mitosis. The same conversion
also proceeds, in a much faster rate, via the direct templation of G2,
confirming the induced-fit transformation mechanism. The structure
4 2
Previously, we introduced a water-soluble Pd L cage 1 with
expanded-size cavity, which can host an increased number of
organic and inorganic guests for selective catalysis.15 We then
wandered whether o-QMs can be stabilized or new reactivity can
be observed for this fleeting species within our water-soluble
Pd
QMs precursor,
Interestingly,
4 2
L cage 1. 1-Hydroxymethyl-2-naphthol (G1), a known o-
12a
2
of the (G2) 2 host-guest complex has been established by X-ray
was chosen as the guest in this work.
guest-reaction induced mitosis-like host
crystallographic study, where cis- to trans- conformational switch on
a
one bridging ligand is revealed.
transformation from cage 1 to an unprecedented conjoined
Pd twin-cage 2 was observed (Scheme 1).
6 3
L
Chemical-triggered structural transformations are commonly
1
observed in biosystems. Moreover, the motions of these natural
systems correspond to essential biological functions, such as
2
ATP synthase. Assembled supramolecular architectures offer
controllable platform at the molecular level to mimic the function
3
of biosystems. Adaptive transformations have also been widely
seen in such artificial hosts with stimuli-responsiveness to
4
5
5a,6
anion, solvent, concentration,
stoichiometric ratio of
post-modification6b,8 chemical fuel9 and so
Guided by the induced-fit mechanism, guest-templated
5f,7
components,
5
f,10
on.
synthesis offers an important route toward otherwise
inaccessible complicated host-guest complexes.5f,11 In this case,
guest molecules with specific sizes, shapes and electrostatic
interactions are usually added to the system from the beginning
to drive the formation of the new complementary complexes.
However, guest-reaction driven structural conversions, i.e. the
new products generated in-situ from the initial added guests
exert the induced-fit power to force the structural transformation
of the host, are extremely rare.11e
o-Quinone methides (o-QMs) are known as a group of
important intermediates in total synthesis of natural products and
pharmaceutical compounds. Due to their biradical or polarized
zwitterion ketene structures, o-QMs are highly reactive toward
Scheme 1. Diagram of (a) cell mitosis and (b) mitosis-like transformation from
cage (G1) 1 to conjoined twin-cage (G2) 2.
4
2
1
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Figure 1. 1H NMR (600 MHz, 298 K) spectra of (a) G1 in DMSO-d
, (b) Cage
O after
6
1
in D
heating at 90 °C for 16 h; (e) (G2)
DOSY spectrum ( : Cage 1; : G1; : G2).
2
O, (c) host-guest complex of (G1)
4
1 in D
2
O; (d) (G1)
4
1 in D
O and (f) its H
2
1
2
2 crystal re-dissolved in D
2
Figure 2. X-ray crystal structure of (G2)
2
2. Cage 2 and guests G2 are
displayed with stick and sphere models respectively (Color code: grey, C; blue,
N; red, O; Cyan, Pd). Distances for host-guest π-π stacking interaction are
indicated. Counter ions and hydrogen atoms are omitted for clarity.
According to our previous reports,15 water-soluble cage 1 was
synthesized from the p-xylene-bridged bis-TPT ligand and the
(
tmeda)Pd(NO
triazine; tmeda= N,N,N',N'-tetramethyl-ethylenediamine). After
different equiv. of G1 were added to cage 1 in D O, formation of
3 2
) capping unit (TPT= 2,4,6-tris(4-pyr-idyl)-1,3,5-
ray crystallography finally established the structure of the new
host-guest complex, which would be extremely challenging to
analyze by other spectroscopic methods. According to the
2
1
a (G1)
4
1 host-guest complex was indicated by H NMR spectra
(
Fig. 1, Fig. S10). Compared to the signals of free G1 (Fig. 1a)
crystal data, the Pd
Pd conjoined twin-cage, with two molecules of 2,2'-dihydroxy-
,1'-dinaphthylmethane (G2) that produced from the self-
4 2
L cage 1 transformed into a brand-new
and empty cage 1 (Fig. 1b), the host-guest complex shows
dramatic changes. Obvious up-field shifts for the naphthalene
signals on G1 from 8.1~7.1 ppm to 6.5~5.4 ppm, and the
methylene signals from 4.9 ppm to 3.7 ppm were observed,
respectively (Fig. 1c). This indicates the efficient guest
encapsulation within the hydrophobic cavity of cage 1. Up to four
molecules of G1 can be encapsulated inside cage 1 based on
6 3
L
1
coupling of the initial G1 guests, sitting inside two independent
cavities (Fig. 2). Without concerning the guests and the
peripheral capping units, cage 1 has a D2d molecular point group
where both ligands adopt the cis- conformation. In contrast,
cage 2 has a low-order C2h symmetry with two cis- and one
trans- ligands coexisting. By one intra-ligand and two inter-
ligands clipping, three TPT panels from one cis-ligand and half
of the bridging trans-ligand defined each hydrophobic cavity of
the twin-cage. Strong π-π stacking interactions between the
naphthalene rings of two independent G2 molecules and the
TPT walls (Fig. 2) were observed, which may have served as
the main driving forces for the induced-fit cage transformation. It
is worth to point out that host structure transformation from one
bigger cavity into two separate smaller cavities, alike the mitosis
of cells, has never been observed before.
the integral ratios from
a
titration experiment (Fig. S11).
Diffusion-ordered 1H NMR spectroscopy ( H DOSY) also
confirmed the formation of a stable host-guest species with a
diameter of 1.59 nm estimated from the Stokes-Einstein
equation (Fig. S12).
1
Interestingly, when the solution of host-guest complex
(G1)
4
1 was heated at 90 °C, dramatic changes were observed
1
in H NMR spectra within 16 h (Fig. 1d, Fig. S13). Characteristic
signals for the encapsulated G1 totally disappeared, along with
the evolution of a new set of splitting signals spanning from 7.6
to 2.3 ppm. Meanwhile, the signature signals of host 1 also
In order to confirm the induced-fit cage transformation
mechanism, independently prepared G2 was treated with cage 1
1
became highly asymmetric. H DOSY confirmed that all the new
signals have the same diffusion coefficient in solution (Fig. S15),
with an apparent larger diameter of 3.58 nm estimated. All of
those changes indicate the transformation of the original
complex into another host-guest complex. The overlapping and
broad nature of the signals indicates that the presence of other
minor species in solution cannot be completely discounted.
Fortunately, brown-red crystals were obtained by slow
(
Fig. 3). An aliquot concentrated solution of G2 in DMSO-d
6
were thoroughly mixed with cage 1 in D O and the suspended
2
1
free G2 was filtered off before taking the H NMR. Based on the
integral ratios from the titration experiments, up to two molecules
of G2 can be encapsulated by cage 1 (Fig. S18-19). Compared
to free G2 (Fig. 3a) and cage 1 (Fig. 3b), the signals of this new
2
(G2) 1 host-guest complex (Fig. 3c) clearly changed with
evaporation of an aqueous solution of (G1)
4
1 at room
and DOSY NMR
measurements after re-dissolving the crystals into D O (Fig. 1e-f,
1
obvious line-broadening, suggesting the slow tumbling motion of
the guests after entering the cavity of cage 1, possibly due to the
large molecular size of G2. Meanwhile, aromatic signals of G2
also witnessed high up-field shifting to 6.5~5.0 ppm, confirming
again a static binding mode of this host-guest complex.
temperature over one month.
H
2
S16-17) confirmed that it was the identical species with the
same diffusion coefficient as obtained by the heating procedure
described above. The crystals were of sufficient quality and X-
2
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and benzene. Competing guest molecules either neutral or
anionic were also screened to kick G2 out of cage 2 (Fig. S33),
but without success. Finally, when the solid of (G2)
2
2 was re-
dissolved in DMSO-d , quick back-transformation to cage 1
6
1
along with severely broadened G2 signals were observed in H
NMR (Fig. S34-36). Moreover, cage 1 could be recycled by the
addition of excess amount of EtOAc to the system to force the
1
precipitation of cage 1, which was confirmed by H NMR in D
2
O
(Fig. S37).
1
Figure 3. H NMR (600 MHz, 298 K) spectra of (a) G2 in DMSO-d
6
, (b) cage 1
in D
0 °C for 40 min (d) (D
first-order kinetic plots for the cage transformation reaction starting from both
2
O, the host-guest complex of (G2)
2
1 in before (c) and after heating at
9
2
O: DMSO-d = 25:1); (e) Conversion and (f) pseudo-
6
(
G1)
4
1 (gray) and (G2) 1 (red) at 90 °C. ( : Cage 1; : G2)
2
Time-dependent 1H NMR spectra were recorded for the
G2) 1 complex. Even at room temperature, distinct signals
2 can be observed after 1 h, indicating the
successful induced-fit transformation of the host (Fig. S19).
When heated to 90 °C, over 60% transformation from (G2) 1 to
G2) 2 was observed within 40 min (Fig. S21-21). Based on
pseudo-first-order reaction kinetics, a 41-fold speed-up for the
rate constant of the G2-driven transformation from cage 1 to
cage 2 was estimated, compared to that of G1 (Fig. 3 e-f; Fig.
S22-23).
Figure 4. Proposed mechanism for the mitosis-like cage 1 to conjoined twin-
cage 2 transformation.
(
2
assignable to (G2)
2
2
(
2
Taken together all the above results and previous reports,16
the following plausible mechanism (Fig. 4) is proposed for this
unique guest reaction driven host transformation process: (1) In
water, up to 4 molecules of G1 were encapsulated by cage 1,
giving rise to a high local concentration of ca. 7.57 M inside the
nano-cavity (Fig. S38). (2) Driven by the hydrophobic effect,
encapsulated G1 undergoes dehydration, giving rise to the o-
QMs intermediates. (3) o-QMs react with another G1 molecules
nearby to form G2, where formaldehyde serves as a leaving
group. Indeed, when DNPH (2,4-dinitrophenylhydrazine) as a
formaldehyde trap was added to the reaction, presence of 2,4-
dinitrophenylhydrazone signals at m/z 210 was clearly detected
by GC-MS (Fig.S41). (4) G2 induced cage 1 to conjoined twin-
cage 2 transformation takes places quickly. (5) Solid-liquid
extraction with an EtOAc/DMSO mixture leads to the recycling of
cage 1 that facilitates the turn-over of the reaction. It worth to
note that though this process, the self-coupling dimerization of
Hydrophobic effect has been noticed to play a key role for
both the encapsulation of G1 and the induced-fit transformation
of cage 1. In a 1:1 (volume ratio) mixed solvent of DMSO-d
6
and
1
D
2
O, H NMR titration indicated that cage 1 has much weaker
binding affinity toward G1, where a continuous down-field
shifting of the guest signal observed (Fig. S26). Fast in and out
exchange has also been clearly seen in the DOSY spectrum,
with two diffusion bands observed for the both the host and the
guest (Fig. S27). Moreover, no obvious change was observed in
1
H NMR after heating the mixture at 90 °C for 16 h (Fig. S28),
indicating that the self-coupling reaction occurred slowly at this
condition. Similar to G1, G2 binding with cage 1 also becomes a
dynamic fast-equilibrium in such mixed solvent condition (Fig.
S29). However, in this case the G2-driven cage 1 to cage 2
transformations can still take place, though with a slower
reaction rate (Fig. S30). We thus conclude that hydrophobic-
driven static encapsulation of G1 is vital for its self-coupling
dimerization reaction within cage 1 (Fig. S31-32).
G1 inside cage 1 is the rate-determining step, thus (G1)
the resting-state which can be observed on the H NMR.
4
1 is
1
In summary, an unprecedented cage to conjoined twin-cage
transformation driven by a self-coupling dimerization reaction of
an o-QMs precursor guest was discovered. To the best of our
knowledge, such a reaction-driven induced-fit cage to twin-cage
transformation has never been observed. This unique molecular
level structural transformation is reminiscent of the cell-mitosis
Due to the strong π-π interactions and the potential
+
deprotonated anionic state of G2 inside the highly 18 charged
cage 2, it turned out to be difficult to extract G2 out of cage 2 by
common water-immiscible organic solvents, such as chloroform
3
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This work was supported by the National Natural Science
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Keywords: Conjoined-Cage • Encapsulation • Guest Reaction •
Cavity Division • Induced-Fit
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355. (b) McConnell, A. J.; Wood, C. S.; Neelakandan, P. P.; Nitschke, J.
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Guest-reaction induced mitosis-like host transformation from Pd
observed.
4 2 6 3
L cage 1 to an unprecedented conjoined Pd L twin-cage 2 was
5
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