Catalytically active nanorotor reversibly self-assembled by chemical signaling within an eight-component network

Article abstract of DOI:10.1039/c8cc01496e

A catalytically active three-component nanorotor is reversibly self-assembled and disassembled by remote control. When zinc(ii) ions (2 equiv.) are added as an external chemical trigger to the mixture of transmitter [Cu(1)]⁺ and pre-rotor assembly [(S)·(R)], two equiv. of copper(i) ions translocate from [Cu(1)]⁺ to the two phenanthroline sites of [(S)·(R)]. As a result, [Zn(1)]²⁺ forms along with the three-component assembly [Cu₂(S)(R)]²⁺, which is both a nanorotor (k₂₉₈ = 46 kHz, ΔH^? = 49.1 ± 0.4 kJ mol^-1, ΔS^? = 9.5 ± 1.7 J mol^-1 K^-1) and a catalyst for click reactions (catalysis ON: A + B→AB). Removal of zinc from the mixture reverts the translocation sequence and thus commands disassembly of the catalytically active rotor (catalysis OFF). The ON/OFF catalytic cycle was run twice in situ in the full network.

Full text of DOI:10.1039/c8cc01496e

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Marilyn M. Olmstead, Alan L. Balch, Josep M. Poblet, Luis Echegoyenet al.
Reactivity differences of Sc3N@C2n (2n 68 and 80). Synthesis of the
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DOI: 10.1039/C8CC01496E
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Catalytically Active Nanorotor Reversibly Self‐Assembled by
Chemical Signaling within an Eight‐Component Network
xxxxxxxxxxxxxxxxxxxx,
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Abir Goswami, Susnata Pramanik and Michael Schmittel*
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A catalytically active three‐component nanorotor is reversibly self‐ allows regulation of both rotational dynamics and catalytic
assembled and disassembled by remote control. When zinc(II) ions activity through chemical signaling and thus represents an
(2 equiv) are added as an external chemical trigger to the mixture example of advanced molecular cybernetics.
of transmitter [Cu(1)]+ and pre‐rotor assembly [(S)•(R)], two equiv
of copper(I) ions translocate from [Cu(1)]+ to the two phenan‐
throline sites of [(S)•(R)]. As a result, [Zn(1)]2+ forms along with
the three‐component assembly [Cu2(S)(R)]2+, which is both a
nanorotor (k298 = 46 kHz, ΔH‡ = 49.1 ± 0.4 kJ mol–1, ΔS‡ = 9.5 ± 1.7 J
mol–1 K–1) and a catalyst for click reactions (catalysis ON: A + B
→AB). Removal of zinc from the mixture reverts the translocation
sequence and thus commands disassembly of the catalytically
active rotor (catalysis OFF). The ON/OFF catalytic cycle was run
twice in situ in the full network.
The time has come to soar above stand‐alone molecular
devices1 and to realize functions2 in complex supramolecular
networks, as ingeniously demonstrated in biological systems.3
For proper administration of emergent properties in multi‐
component ensembles, though, accurate signaling4 is needed
which calls for both selectivity and orthogonality5 in communi‐
cation. The high utility of essential metal ions, such as cop‐
per(I,II) and iron(II) ions, for cell signaling has become evident
recently.6 Yet, the use of metal ion flux for communication is
poorly exploited in (supra)molecular signaling,7 although it
allows selective networking of artificial molecular devices.
Scheme 1. Cybernetic network between nanoswitch [Cu(1)]+ and nanorotor
[Cu2(S)(R)]2+ activated by addition of zinc(II) ions.
The design for the multifunctional cybernetic system in
Scheme 1 was based on the following considerations: (1) both
the nanoswitch and the nanorotor’s components must not
interfere with each other in any network state (NetState). (2)
The metal‐ion translocation between nanoswitch and the
constituents of the nanorotor should be harmonized in both
directions. (3) In the initial self‐sorting, the copper(I) ions need
to be more weakly bound to the nanorotor’s constituents than
to the nanoswitch. (4) The nanoswitch must have a higher
binding affinity towards the external trigger input so that the
liberated copper(I) ions will set up the self‐assembled nano‐
rotor and turn ON catalysis. (5) Equally central is the choice of
reactants and products in the catalytic reaction, so that there
is no interference with the full system.
Recently, we established a regulated network of two
triangular nanoswitches based on copper(I)‐ion transfer8 in
response to an external trigger (= iron(II) ions) which enabled
ON/OFF control over a catalytic reaction.8a In the present work
we will demonstrate how self‐assembly and disassembly of a
catalytically active three‐component nanorotor is commanded
by chemical communication within an ensemble of eight
distinct components. This smart networked nanomachinery
Center of Micro and Nanochemistry and Engineering, Organische Chemie I,
Universität Siegen, Adolf‐Reichwein‐Str. 2, D‐57068 Siegen, Germany
E‐mail: schmittel@chemie.uni‐siegen.de; Tel: +49(0) 2717404356
Electronic Supplementary Information (ESI) available: Experimental procedures,
compound characterizations, spectral data, UV‐vis titrations data. See
DOI: 10.1039/x0xx00000x
In response to considerations (1)‐(5) we have selected
nanoswitch 19 (Scheme 1) because it demonstrated a higher
binding affinity (∆log K = 2.7) toward zinc(II) (ESI†, Fig. S45)
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than toward copper(I) ions (ESI†, Fig. S44). Based on recent 2). Kinetic analysis provides the exchange freqVuieewnAcryticle(kO)nlianet
experience,10 we came up with a new design for the nanorotor different temperatures (Figure 4a), withDkO2I9:810=.140369/kCH8zCC(a0t1429968E
[Cu2(S)(R ,
)]2+. It is based on stator S 11 in which two shielded K). The activation data are ΔH‡ = 49.1 ± 0.4 kJ mol–1, ΔS‡ = 9.5 ±
phenanthrolines (phenAr2) are connected to a zinc porphyrin 1.7 J mol–1 K–1 and ΔG‡298 = 46.6 kJ mol–1 (ESI†, Fig. S32).
Experimental Simulated
(ZnPor), and rotator
Both parts are expected to weakly coordinate thus forming the
R with two identical pyridyl terminals.
*
*
*
*
*
pre‐rotor [(S)•(R)] through pyridine → zinc porphyrin binding
k =
k =
12 Hz
12 Hz
*
-60 °C
-50 °C
*
-60 °C
(Npy → ZnPor, log K =3.8).12 Finally, addition of two equiv of
copper(I) ions ought to furnish the three‐component nano‐
*
*
*
45 Hz
45 Hz
*
*
-50 °C
-40 °C
*
rotor [Cu2(S)(R
)]2+ due to Npy → [Cu(phenAr2)]+ binding (=
*
160 Hz
k = 160 Hz
HETPYP13 binding, log K = 3.2).10
-40 °C
-25 °C
0 °C
*
*
*
*
k =
k =
930 Hz
780 Hz
-25 °C
0 °C
*
*
*
*
7.2 kHz
7240 Hz
*
*
25 °C
46 z
k = 458kH00 H
25 °C
9.0
8.8 8.6
9.00 8.88
9.00 8.88
Figure 2. Experimental and theoretical splitting of phenanthroline proton 4´‐H of nano‐
rotor [Cu2(S)(R)]2+ in VT 1H‐NMR (600 MHz) furnishing rate data in CD2Cl2.
Figure 1. Partial 1H‐NMR (400 MHz, CD2Cl2, 298 K) of (a) rotator (R), (b) stator (S), (c)
For the mechanism of exchange two plausible alternatives
may be considered: (i) an intramolecular non‐directional rota‐
[(S)•(R)], (d) nanorotor [Cu2(S)(R)]2+
.
tion requiring the dissociation/association of one Npy
→
[Cu(phenAr2)]+ in the rate‐limiting step or (ii) a complete disso‐
Preparation of the three‐component assembly [Cu2(
was readily accomplished by mixing [Cu(CH3CN)4]PF6 & ligands
and in 2:1:1 ratio in d2‐dichloromethane at 25 °C. The dark
S)(R
)]2+
ciation of [Cu2(S)(R S R by cleavage of both
)]2+ into [Cu2( )]2+ and
the Npy → [Cu(phenAr2)]+ and Npy → ZnPor interactions fol‐
lowed by reassociation. Because full dissociation is endergonic
by ΔG°298 = 40.6 kJ mol–1 (derived from log K = 7.13), which is
S
R
violet product is readily characterized by spectroscopic data
1
(1H NMR, H‐1H COSY, UV‐vis, ESI‐MS) and elemental analysis.
smaller than the kinetic barrier of ΔG‡
= 46.6 kJ mol–1, the
For instance, a single peak at m/z = 1245.1 in the electrospray
ionization mass spectrum (ESI‐MS) attests the formation of
298
mechanisms cannot be differentiated thereby. However, the
)]2+ are very similar to
[Cu2(
[Cu2(
S
S
)(
)(
R
R
)]2+ (ESI†, Fig. S37). In the 1H NMR spectrum of
kinetic data for exchange in [Cu2( )(
S
R
)]2+ notable downfield shifts of the phenanthroline
those of previously reported nanorotors that operate via a sin‐
gle Npy → [Cu(phenAr2)]+ dissociation (ΔG‡298 = 48.3 kJ mol–1).14
This good agreement suggests that the exchange mechanism
protons 4´‐H, 5´‐H, 6´‐H, and 7´‐H verify the Npy
→
[Cu(phenAr2)]+ complexation whereas upfield shifts of the
in [Cu2(S)(R
)]2+ involves rotation with the Npy → ZnPor
porphyrin β‐H protons indicate the axial Npy → ZnPor
coordination (Figure 1). While stator
displays an absorption at λ = 422 nm, the axial Npy → ZnPor
coordination in [( )•( )] leads to an absorption at λ = 426 nm
(ESI†, Fig. S42). Finally, in [Cu2( )]2+ the Soret band is located
)(
at λ = 429 nm (ESI†, Fig. S42). A UV‐vis titration allowed
determination of the overall association constant between
S as a separate molecule
interaction kept intact and the second pyridine terminal of
R
exchanging between the two [Cu(phenAr2)]+ sites.
S
R
For controlling the assembly and disassembly of
[Cu2( )(
)]2+ by metal ion flux through remote control, we de‐
cided to test nanoswitch [Cu(
)]+ for its ability to reversibly
transmit/receive copper(I) ions to/from the pre‐rotor/rotor
assembly. The ferrocene and mesityl protons of (Figure 3)
serve as diagnostic H NMR reporters for metal‐ion exchange
S
R
S
R
1
R
and [Cu2(S
)]2+ (log K = 7.13 ± 0.28; see ESI†, Fig. S43). Finally, a
1
single set of 1H‐DOSY signals (D = 3.6 × 10−10 m2 s−1, r ~14.7 Å)
proves the clean formation of the assembly (ESI†, Fig. S30). Im‐
portantly, the single set of 1H NMR signals for both
phenanthroline units is indicative of a dynamic system.
1
1
(copper(I) vs zinc(II) ions).9 In the H NMR of [Cu( )]+, the fer‐
1
rocene protons lose their symmetry and shift upfield to 3.32,
3.67, 4.54 and 4.92 ppm in d2‐dichloromethane (ESI†, Fig. S18).
The mesityl protons also shift upfield to 6.35 and 6.43 ppm. In
Analogous exchange of dynamic Npy
→
[Cu(phenAr2)]+
the other switching state, [Zn(1
)]2+ the ferrocene protons
interactions was previously seen in speed‐regulated four‐ and
five‐component nanorotors.10
appear at 3.35, 3.84, 4.37, 5.48 ppm and mesityl protons shift
to 6.03 and 6.43 ppm in 5:1 CD2Cl2:CD3CN (ESI†, Fig. S19).
To establish reversible networking between transmitter
In order to measure the exchange frequency in nanorotor
[Cu2(S)(R
)]2+, we analyzed the signal (Figure 2) of phenanthro‐
)]+ and the pre‐rotor [(
S
R)], we first prepared NetState
line proton 4´‐H that shows up as a sharp singlet (8.96 ppm) at
25 °C in VT 1H NMR studies. Diagnostically, at –60 °C it
separates into two singlets (1:1) at 8.93 and 8.89 ppm. The sig‐
nal at 8.89 ppm corresponds to the pyridine‐coordinated
phenanthroline station, the freely rotating [Cu(phenAr2)]+
station furnishes a slightly broader signal at 8.93 ppm (Figure
[Cu( )•(
1
I
by mixing 1, S, R and [Cu(CH3CN)4]PF6 in 2:1:1:2 ratio in d2‐
dichloromethane at 25 °C resulting in a dark violet solution. In
the ESI‐MS a major peak at m/z = 1156.0 (100%) attests the
formation of nanoswitch [Cu(1
)]+ with its isotopic distribution
exactly matching the theoretical one (ESI†, Fig. S40). Diagnosti‐
2 | J. Name., 2017, 00, 1‐3
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1
cally shifted ferrocene and mesityl proton signals in the H shifted immediately from λ = 429 to 426 nm (ESI†V,ieFwigAr.ticSle4O6n)lianet
DOI: 10.1039/C8CC01496E
NMR suggest that the copper(I) ions quantitatively bind to 25 °C. Apparently, the hexacyclen first captures the copper(I)
nanoswitch
1
as anticipated (ESI†, Fig. S21). In chorus, the pre‐ ions before exchanging metal ions with switch
1.
rotor [( )•(R)] assembles by intermolecular Npy → ZnPor axial Notwithstanding the complex metal ion exchange mechanism,
S
coordination, as documented by the Soret band showing up at quantitative and reversible switching between NetState I and
λ = 426 nm in the UV‐vis spectrum (ESI†, Fig. S46).
II was demonstrated over three cycles (ESI†, Fig. S22).
To generate NetState II we added 2.0 equiv of Zn(OTf)2 (as
a standard solution in CD3CN) to NetState I at 25 °C. Both, ESI‐
1
MS and H NMR data (Figure 3b) confirm quantitative forma‐
tion of [Zn(1 S)(R
)]2+ and nanorotor [Cu2( )]2+. In the ESI‐MS we
observe a singly charged species at m/z = 1307.3 (85%) and a
doubly charged one at m/z = 578.6 (60%) both reflecting the
presence of [Zn(
anions, respectively (ESI†, Fig. S41). Another doubly charged
species at m/z = 1245.2 (100%) represents [Cu2( )(
)]2+ (ESI†,
Fig. S41). Diagnostic H NMR shifts confirm the presence of
both complexes [Cu2( )(
)]2+ and [Zn( )]2+ (ESI†, Fig. S21). Ac‐
cordingly, addition of zinc(II) ions to NetState I has prompted
[Cu(
)]+ to deliver copper(I) ions to both empty phenAr2 sites
of the pre‐rotor. As a result, the free pyridyl terminal of
forms a Npy→ [Cu(phenAr2)]+ linkage (HETPYP complex), which
finalizes the assembly of nanorotor [Cu2( )(
)]2+.
1
)]2+ after loss of one and two OTf− counter
S
R
1
S
R
1
1
R
S
R
Figure 4. (A) Time dependence of Cu+ translocation (1.8 mM, CD2Cl2, at 298 K) after
adding Zn(OTf)2 to a solution of NetState I. 1H NMR spectra (400 MHz, CD2Cl2:CD3CN =
5:1) recorded at different times. (B) Intermediate [Zn2(S)(R)]4+ prior to metal exchange.
(C) Formation of NetState II with time.
Despite the copper(I) ions being dynamically tri‐coordina‐
ted (HETPYP13 complexation), the nanorotor [Cu2( )]2+ (ge‐
S)(R
nerated in NetState II) may have the potential to catalyze a
click reaction. In contrast, NetState I is expected to shut down
any catalysis because Cu+ is tightly kept in the binding cavity of
Figure 3. Partial 1H NMR spectra (400 MHz, CD2Cl2, 298 K) showing the reversible
switching between NetState I and II over 2.5 cycles. (a) After mixing of [Cu(CH3CN)4]PF6,
switch 1, S, and R in 2:2:1:1 ratio (NetState I); (b) after adding 2.0 equiv. of Zn(OTf)2 in
CD3CN furnishing [Zn(1)]2+ and [Cu2(S)(R)]2+ (NetState II); (c) NMR after addition of 2.0
equiv. of hexacyclen regenerating NetState I. Mesityl protons now show up as a broad
singlet at 6.36 ppm due to added CD3CN; (d) addition of 2.0 equiv. of Zn(OTf)2
regenerates NetState II; (e) after addition of 2.0 equiv. of hexacyclen.
1
. To test this hypothesis, a mixture of 2‐azido‐1‐(4‐nitrophe‐
nyl)ethanone ( ) and ethynylbenzene ( ) (1:5) in CD2Cl2:CD3CN
= 5:1 was heated at 50 °C for 2 h in presence of 5 mol% of
A
B
nanorotor [Cu2(S)(R
)]2+, furnishing the click product AB in
(37±1)% yield (ESI†, Fig. S25). A control experiment at identical
reaction conditions afforded no product in presence of 10
The kinetics of the copper(I) ion translocation (NetState I
mol% of nanoswitch [Cu(1
)]+ (ESI†, Fig. S26). Equally, free cop‐
→
II) was investigated by UV−vis spectroscopy. Upon addition
per(I) ions are not responsible for product formation, because
a speciation distribution analysis indicates that only 6% of cop‐
per(I) is free in solution and thus <2% of AB may arise there‐
from (ESI†, Fig. S47). This finding clearly indicates that nano‐
of 2.0 equiv of Zn(OTf)2, the Soret band absorption shifted in‐
stantaneously from λ = 426 to 429 nm (ESI†, Fig. S46). How‐
ever, 1H NMR analysis indicates that the overall process is not
that fast: it takes close to 2 h for complete translocation at 25
°C (Figure 4A). Accordingly, at first the added zinc(II) ions fill
rotor [Cu2(S)(R
)]2+ is the active catalyst.
the phenanthroline sites of [(
which is the cause for the immediate shift of the Soret band.
Then in the slow step [Zn2( )(
)]4+ + 2×[Cu( )]+ → 2×[Zn( )]2+
[Cu2( )(
)]2+ the metal ions exchange their positions to furnish
S)•(R)] furnishing [Zn2(S)(R
)]4+,
Finally we studied the fully networked catalytic machinery
in an ON/OFF manner (ESI†, Fig. S28). For that purpose, Net‐
State I was prepared as before and mixed with substrates
A
S
R
1
1
+
and in 1: 10 : 50 ratio in d2‐dichloromethane/CD3CN = 5:1.
B
S
R
The mixture was heated for 2 h at 50 °C, but no conversion
was detected (Figure 5a,b). Obviously, the copper(I) ions are
the thermodynamically preferred NetState II (Figure 4B). To
reverse the reaction, we added 2.0 equiv of hexacyclen as a
strong chelating agent to NetState II at 25 °C. After only 5 min,
buried in nanoswitch [Cu(1
)]+ (ESI†, Fig. S28) and thus remain
there was no more diagnostic signal for [Zn(1
)]2+ left in the 1H
catalytically inactive. Now 2.0 equiv of zinc(II) ions were added
as a standard solution in acetonitrile‐d3 (75 µL) to generate
NetState II. The mixture was then heated as before for 2 h at
NMR and all NMR shifts were fully matching with those of
NetState I (Figure 3c). Parallel in a UV‐vis study, the Soret band
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50 °C and (36±1)% of product AB (ESI†, Fig. S28) was detected
in H NMR (yield from three independent runs). Notably, the
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catalytic activity of the nanorotor was the same as that of the
model reaction in the absence of [Zn(1
)]+. To turn OFF the
reaction, 2.0 equiv of hexacyclen and the consumed amounts
of substrates were added to achieve similar reaction condition.
After heating for another 2 h using the same conditions, an
1
extra (1.6±0.7)% of product AB was detected in H NMR. This
finding suggests that the copper(I) ions have translocated back
to nanoswitch
1 so that they are not available for catalyzing
the click reaction. A second cycle furnished similar results (ON:
(36±2)%; OFF: 0% ) reflecting a remarkable reproducibility of
communication and operation within the networked catalytic
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Figure 5. (A) Representation of the ON/OFF regulation of the click reaction in NetState I
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amounts of the click product AB in NetState II (three independent runs). Consumed
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addition/removal of zinc(II) ions commands nanoswitch
1 to
transmit/receive copper(I) ions that serve as a second messen‐
ger. In the forward process, the copper(I) ions assemble a
catalytically active three‐component nanorotor from a weakly
bound precursor complex, in the back process the disassembly
leads to a catalytically inactive ensemble. This illustration of
molecular cybernetics is a step toward the integral control of
different molecular devices16 operating not any more as indivi‐
duals but as intricate (supra)molecular machinery. It nicely
complements present efforts to run molecular machines using
off‐equilibrium conditions,17 so that in the future not only
single machines but also networked multi‐component machi‐
nery may run on chemical fuel.
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We thank the DFG (Schm 647/19‐2 and 647/20‐1) and the
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4 | J. Name., 2017, 00, 1‐3
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