Formation of Functional Cyclooctadiene Derivatives by Supramolecularly- Controlled Topochemical Reactions and Their Use as Highly Selective Fluorescent Biomolecule Probes?

Article abstract of DOI:10.1002/cjoc.202000125

Controlling the regio- and stereochemistry of the photoproducts in solution is far more challenging for polyenes than for monoalkenes. Herein, a supramolecularly-controlled topochemical reaction of conjugated dienes in homogeneous system is developed, ultimately providing two cyclooctadiene-cored tetraimidazolium molecular receptors exclusively. These cyclooctadiene derivatives exhibited highly sensitive and selective fluorescence sensing for thymine relative to other biologically relevant species in aqueous solution at physiological pH. Both the cyclooctadiene moieties and imidazolium units play important roles in the selective recognition observed. The presented supramolecularly-controlled method allows the simple yet rare selective photoconversion of flexible cyclooctadiene derivatives in solution. This study offers a new synthetic strategy for the preparation of functional molecules with potential for use in biological applications.

Full text of DOI:10.1002/cjoc.202000125

Chinese Journal
of Chemistry
CJC
中 国 化 学 - An International Journal
Accepted Article
Title: Formation of Functional Cyclooctadiene Derivatives by Supramolecularly-
Controlled Topochemical Reactions and Their Use as Highly Selective Fluorescent
Biomolecule Probes
Authors: Ming-Ming Gan, and Ying-Feng Han*
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This work may now be cited as: Chin. J. Chem. 2020, 38, 10.1002/cjoc.202000125.
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Formation of Functional Cyclooctadiene Derivatives by
Supramolecularly-Controlled Topochemical Reactions and Their Use as
Highly Selective Fluorescent Biomolecule Probes
Ming-Ming Gan,a and Ying-Feng Han*,a,b
aKey Laboratory of Synthetic and Natural Functional Molecule Chemistry, College of Chemistry and Materials Science, Northwest University, Xi’an 710127,
P. R. China
bState Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002,
P. R. China
Cite this paper: Chin. J. Chem. 2019, 37, XXX—XXX. DOI: 10.1002/cjoc.201900XXX
Summary of main observation and conclusion Controlling the regio- and stereochemistry of the photoproducts in solution is far more challenging for
polyenes than for monoalkenes. Herein, a supramolecularly-controlled topochemical reaction of conjugated dienes in homogeneous system is developed,
ultimately providing two cyclooctadiene-cored tetraimidazolium molecular receptors exclusively. These cyclooctadiene derivatives exhibited highly
sensitive and selective fluorescence sensing for thymine relative to other biologically relevant species in aqueous solution at physiological pH. Both the
cyclooctadiene moieties and imidazolium units play important roles in the selective recognition observed. The presented supramolecularly-controlled
method allows the simple yet rare selective photoconversion of flexible cyclooctadiene derivatives in solution. This study offers a new synthetic strategy
for the preparation of functional molecules with potential for use in biological applications.
for biomolecular sensing.
Background and Originality Content
Due to their effective binding with guest species through ionic
Template-controlled supramolecular synthesis (e.g. those using
coordination bonds, hydrogen bonds, halogen bonds, cation···π,
π···π, and halogen···halogen interactions) has been found to be a
useful method to align pairs of C=C bonds to meet Schmidt’s
postulate and allow photochemical reactions to proceed.
However, most of these photoreactions were limited to the solid
or crystalline states.[1-3] The control of the regio- and
(C-H)+···A−
hydrogen-bonding
interactions,
fluorescent
imidazolium-based receptors have been extensively investigated
in recent years due to their simplicity and the high sensitivity
afforded by changes in their fluorescence intensity.[12] The scope
Scheme 1 Possible photoproducts obtained by the photoreaction of
symmetrical diene
stereoselectivity
of
photo-induced
transformations
in
A
A
A
A
homogeneous solutions remains a significant challenge, with
limitations related to the solubility of the supramolecular
assemblies, maintaining the appropriate orientation of the
conjugated C=C bonds and the formation of mixtures of
compounds due to cis-trans-isomerization.[4]
The scope of the substrates used in photochemical reactions of
this type is largely limited to monoalkenes, as polyenes have
multiple reactive sites, opening the possibility of [2+2] or [4+4]
cycloaddition reactions or other reactions, and thus the potential
formation of a number of regio- and stereoisomers, E/Z isomers,
and even polymers (Scheme 1).[5-7] Therefore, controlling the
regio- and stereochemistry of the photoproducts is far more
challenging for polyenes than for monoalkenes.[8,9] Recently, we
A
A
A
A
A
(a)
(b)
hv
A
(e) Polymers
2
A
A
A
A
A
A
A
A
(c)
(d)
of application of imidazolium-based receptors in sensing is often
limited to small anions, with the exception of a few examples
describing the sensing of biomolecules.[13,14] Indeed, it is still
challenging to design scaffolds for the specific recognition of
biologically relevant targets, especially host molecules that are
soluble in aqueous solution at physiological pH. Herein, we
supramolecularly-controlled topochemical
photoreaction in solution that provides two cyclooctadiene-cored
tetraimidazolium receptor molecules. Due to their flexible
developed
a
strategy for the preparation of
a
series of
applying
polyimidazolium
cyclobutane derivatives by
metal-carbene template-directed [2+2] cycloaddition reactions in
homogeneous solution.[10,11] We expected this method to be
applicable for the construction of functional molecules of
increasing structural complexity; our goal was not only to utilize
this metal-carbene-templated photochemical reaction to
generate new complexes but also to produce functional receptors
demonstrate
a
This article has been accepted for publication and undergone full peer review but has not been
through the copyediting, typesetting, pagination and proofreading process which may lead to
differences between this version and the Version of Record. Please cite this article as doi:
10.1002/cjoc.202000125
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Gan et al.
Report
cyclooctadiene moieties and imidazolium-based receptor sites,
the cyclooctadiene derivatives exhibit highly sensitive and
selective fluorescence sensing for thymine relative to other
relevant molecules in aqueous solution at physiological pH (7.4).
The key step in the synthesis of the receptor is the formation of a
cyclooctadiene ring by a photo-induced topochemical reaction
facilitated by supramolecular templates. A series of dinuclear AgI
and AuI molecular rectangles featuring dienyl-bridged dicarbene
ligands were designed and synthesized, wherein the
preorganization of the pairs of dienyl units brings them into close
enough proximity to allow further photochemical modification
(Scheme 2). Facile removal of the metal ions by cleavage of the
metal-carbene bond then affords cyclooctadiene-cored
tetraimidazolium compounds. This supramolecularly-controlled
method allows the simple yet rare selective photoconversion of
flexible cyclooctadiene derivatives in solution.
Results and Discussion
Bis(imidazolium)-substituted diene derivatives H2-L(PF6)2 (L = 2a,
2b) were prepared from (1E,
3E)-1,4-bis(4-(1H-imidazol-1-yl)phenyl)buta-1,3-diene (1)[15] using
a similar reported procedure (see Supporting Information (SI),
Scheme S1).[11d] The 1E,3E structure of the proligand was
confirmed by X-ray diffraction analysis of crystals of H2-L(PF6)2
(Figure 1). As shown in Scheme 2, the dinuclear tetracarbene
complexes [Ag2(L)2](PF6)2 (L = 2a, 2b) were synthesized in
excellent yields by the reaction of bisimidazolium salts H2-L(PF6)2
(L = 2a, 2b) with excess Ag2O in acetonitrile at 65 °C for 48 h under
the exclusion of light (see SI).
In contrast to the proligands H2-L(PF6)2, the characteristic
resonances of the C2-H protons of the imidazolium salts were not
observed in the 1H NMR spectra of silver(I) carbene complexes
[Ag2(L)2](PF6)2 (L = 2a, 2b) (Figure 2a,c and S1). In the 13C{1H} NMR
spectra of the complexes, characteristic CNHC resonances for
[Ag2(2a)2](PF6)2 and [Ag2(2b)2](PF6)2 were observed at δ = 178.1
and 178.3 ppm, respectively, which are typical values for silver(I)
carbene complexes. The electrospray ionization mass spectra
(ESI-MS) in positive mode further supported the formation of the
silver(I) complexes. For example, the ESI-MS spectra showed
peaks at m/z = 502.1441 (calcd for [Ag2(2a)2]2+ 502.1204) and m/z
= 558.1842 (calcd for [Ag2(2b)2]2+ 558.1831) (see SI).
Scheme 2 Preparation and reactions of dicarbene-derived metallacycles to
afford cyclooctadienes
2 PF6
R
R
R
c
4
Cl
N
N
N
c
N
N
N
Gold(I) carbene complexes [Au2(L)2](PF6)2 (L = 2a, 2b) were
synthesized by treating the corresponding silver(I) carbene
complexes [Ag2(L)2](PF6)2 with 2 equiv of [AuCl(THT)] (THT =
tetrahydrothiophene) in acetonitrile at ambient temperature for
24 h under exclusion of light (Scheme 2). These gold(I) complexes
were isolated as air- and moisture-stable off-white solids in yields
of 82% and 79%, respectively. Both complexes were fully
characterized by NMR spectroscopy and ESI-MS analysis (see SI).
The structure of [Au2(2a)2](PF6)2 was further confirmed by X-ray
diffraction (Figure 3). The gold(I) atoms are coordinated to the
NHC ligands in a linear fashion with CNHC−Au−CNHC angles of 173.7
and 176.2°, and Au−CNHC distances between 1.996 and 2.042 Å.
The Au−NHC bonds of this gold(I) complex bring the diene
moieties into closely proximity in a “face-to-face” manner with
distances between the pairs of olefin C=C bonds of ca. 4.2 Å.
b
b
via
templates
introduce
metal-carbene bond formation
i)
a
a
ii)
reaction in solution
topochemical
removal
diene
cyclooctadiene
iii)
via
templates
metal-carbene bond cleavage
N
N
N
N
N
N
R
R
R
=
=
-
-
=
2a
Et, H2
R
R
R
Et, H4 3a
(Cl)4
(PF6)2
-
nBu, H2
-
nBu, H4 3b
=
2b
R
(PF6)2
Ag
(Cl)4
2O
CH3CN, 65 o 48
i)
h
iii) NH4Cl
C,
R
N
R
2 PF6
R
R
N
2 PF6
N
N
Ag
M
N
N
N
N
b
b
a
a
nm
ii) hv 365
,
Figure 1 ORTEP view of ligand H2-2a(PF6)2 with 50% ellipsoid probability
and hydrogen atoms omitted for clarity. Selected bond lengths (Å) and
angles (deg): N(1) −C(3) 1.326(2), N(2)−C(3) 1.336(2), C(10)−C(12) 1.463(2),
C(12)−C(13) 1.337(2), C(13)−C(13#) 1.447(3); N(1)−C(3)−N(2) 108.44(13),
C(13)−C(12)−(C10) 126.90(15).
solution
N
N
N
N
N
Ag
M
N
R
N
N
R
R
R
=
2a
=
=
R
Et,
3a
[M2( )](PF6)2
R
R
Et,
[Ag2( )2](PF6)2
R
nBu,
Ag,
=
M
Au
=
2b
iv)
CH3CN,
[Ag2( )2](PF6)2
AuCl(THT)
rt, 24 h
nBu,
3b
[M2( )](PF6)2
=
=
2a
R
R
Et,
nBu,
[Au2( )2](PF6)2
=
M
Au
Ag,
2b
[Au2( )2](PF6)2
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Running title
Chin. J. Chem.
Figure 2 1H NMR spectra (400 MHz, 298 K, [D6]DMSO) of complexes.
Partial 1H NMR spectra of H2-2a(PF6)2 (a) before and (b) after UV
irradiation; of [Ag2(2a)2](PF6)2 (c) before and (d) after irradiation; and of (e)
H4-3a(Cl)4.
Figure 3 X-ray structure of [Au2(2a)2](PF6)2 (top) ORTEP view with 50%
ellipsoid probability and (bottom) side view. Anions and hydrogen atoms
omitted for clarity. Selected bond lengths (Å) and angles (deg): C13−C12
1.337(15), C14−C13 1.433(15), C15−C14 1.330(15), C38−C39 1.332(16),
C40−C39 1.452(16), C41−C40 1.318(17), Au1−C5 2.020(12), Au1−C50
2.025(13), Au2−C24 2.042(12), Au2−C31 1.996(11); C5−Au1−C50 173.7(5),
C31−Au2−C24 176.2(4).
Photoreaction of [M2(L)2](PF6)2 (M = Ag, Au; L = 2a, 2b) in
[D6]DMSO at ambient temperature with a Xe lamp (λ = 365 nm)
revealed
the
clear
formation
of
corresponding
cyclooctadiene-carbene complexes [M2(L)](PF6)2 (M = Ag, Au; L =
3a, 3b) in nearly quantitative conversion, respectively (Figure 2,
S1-3). All complexes were well characterized by multinuclear NMR
spectroscopy and ESI-MS spectrometry. In a typical experiment,
the formation of cyclooctadiene-carbene complexes can be
reliably monitored by 1H NMR spectroscopy. For example,
doublet resonances for the diene protons of Ha and Hb in
[Ag2(2a)2](PF6)2, at δ = 7.20 and 6.88 ppm, are not observed in
[Ag2(3a)](PF6)2 after irradiation. Instead, a new characteristic pair
of relatively high-field proton signals at δ = 6.23 and 4.88 ppm in a
1:1 intensity ratio confirmed the assignment of the
cyclooctadiene-containing structure of the silver(I) carbene
complexes (Figure 2c,d). The 13C{1H} NMR spectrum of
[Ag2(3a)](PF6)2 further verified the formation of the
cyclooctadiene ring with characteristic resonances at δ = 131.3
and 49.5 ppm. To investigate this irradiation progress further, we
collected aliquots of the mixture of [Ag2(2a)2](PF6)2 under UV
irradiation at various time intervals and acquired their 1H NMR
spectra, (Figure S4) which indicated the gradual disappearance of
the diene resonances and appearance of two new peaks for the
cyclooctadiene ring (but no other new signals corresponding to
intermediate [2+2] cyclobutane products) and that the
photoreaction was completed in 80 mins. In addition, the
conversions were also monitored by UV-vis, fluorescence and IR
experiments (Figure S5-9).[16]
Testing this reaction in the absence of the metal-carbene
template, no [4+4] or [2+2] cycloaddition products were formed
by treating the proligand H2-2a(PF6)2 under the same conditions,
even with extension of the irradiation time to 8 h (Figure 2b).
These results demonstrate that two pairs of conjugated olefins
possess comparable photochemical reactivity and that the
exclusive formation of the cyclooctadiene product is obviously
controlled by steric restriction upon metal-carbene rigidification
within the metallarectangle architecture. The cyclooctadiene
tetraimidazolium salts H4-L(Cl)4 (L = 3a, 3b) were subsequently
isolated by the removal of the silver cations by treatment with
1
NH4Cl in methanol and removal of the precipitated AgCl. The H
NMR spectrum of H4-3a(Cl)4 showed broad peaks that can be
explained by the flexibility of the cyclooctadiene rings and the
inequivalent protons of the phenylene rings and imidazolium
units (Figure 2e). The ESI-MS data provided further evidence for
the formation of the desired tetraimidazolium salts.
A biomolecule recognition experiment was conducted by
measuring the fluorescence variation of the imidazolium salt
Chin. J. Chem. 2019, 37, XXX－XXX
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Gan et al.
Report
H4-3a(Cl)4 (30 μM) upon addition of 20 equiv of a variety of
biomolecules under physiological conditions (10 mM phosphate
buffer at pH = 7.4) at λex = 282 nm. As shown in Figure 4, the
fluorescence of H4-3a(Cl)4 was significantly quenched upon the
addition of thymine (T). In contrast, only minor changes were
observed upon addition of 20 equiv of a series of amino acids,
such as homocysteine (Hcy), alanine (Ala), proline (Pro), threonine
(Thr), glycine (Gly), leucine (Leu), isoleucine (Ile), valine (Val),
serine (Ser), asparagine (Asn), phenylalanine (Phe), penicillamine
Figure 4 Fluorescence responses of hosts to biomolecules. (a) Schematic
representation of the binding interaction between H4-3a(Cl)4 and
biological species. (b) The inorganic anions and biomolecules in this study.
(c) Fluorescence responses of H4-3a(Cl)4 (30 μM) to various biomolecules
at pH = 7.4 (10 mM phosphate buffer) (excitation at 282 nm). The bars
represent the fluorescence responses (λem = 390 nm) upon addition of 20
equiv of the respective biomolecule. (d) Fluorescence responses of
H4-3a(Cl)4 (30 μM) at λem = 390 nm with 20 equiv of the respective anion
species. (e) Fluorescent emission changes of H4-3a(Cl)4 (30 μM) upon
addition of T, U, G, A, and X (20 equiv) at pH = 7.4 (10 mM phosphate
buffer). (d) Fluorescence responses of different hosts (30 μM) to
biomolecules at pH = 7.4. I and I0 was the fluorescence intensity of the
H4-3a(Cl)4 only and the H4-3a(Cl)4 after guest added.
(Pen), cysteine (Cys), methionine (Met), arginine (Arg) and
histidine (His). No obvious change was observed upon addition of
excess glutathione (GSH), fructose (Fru) or glucose (Glc) (Figure
4c). Furthermore, only minor changes were observed upon
addition of 20 equiv of different inorganic anion species, including
–
–
–
–
F–, Cl–, Br–, I–, CO32–, HCO3 , HSO3 , SO32–, S2O32–, NO3 , NO2 ,
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Running title
Chin. J. Chem.
–
H2PO4 , HPO42–, PO43– (Figure 4d).
solution. Moreover, the cyclooctadiene imidazolium derivatives
can be applied as fluorescent chemosensors that sense thymine
selectively through fluorescence quenching over other biologically
relevant biomolecules in aqueous solution of physiological pH
(7.4). In the future, we hope to realize the application of this type
of photoproducts for detecting biologically relevant targets (such
as nucleic acids), which would mark a significant achievement in
the field of host-guest systems. We anticipate that the present
method could serve as a new tool in the synthesis of unique
functional molecules with potential applications in biological
studies.
To further evaluate whether H4-3a(Cl)4 exhibits high selectivity
for thymine, the fluorescence changes were measured upon
addition of the structurally similar biomolecules including uracil
(U), guanine (G), adenine (A), xanthine (X). Surprisingly, each of
these species induced almost negligible changes compared to that
caused by thymine (Figure 4e). Competitive binding experiments
were also conducted in the presence of different inorganic anions
and uracil (U) at 20 equiv, respectively, with the subsequent
addition of 20 equiv of thymine (Figure S10,11). No significant
variation in the fluorescence intensity was observed except for
with thymine.
To our surprise, no selectivity for thymine over other
biomolecules was observed when bisimidazolium salt H2-2a(Br)2
or cyclobutane-based tetraimidazolium salt (4) were used as
receptor under the above conditions (Figure 4f, S12). These
results imply that both the cyclooctadiene and imidazolium units
play important roles in the selective recognition for thymine,
however, the binding mode in solution needs to be confirmed by
further detailed investigations.
Supporting Information
The supporting information for this article is available on the
WWW under https://doi.org/10.1002/cjoc.2019xxxxx. CCDC
1976920
and
1976922
contain
the
supplementary
crystallographic data for this paper. These data are provided free
of charge by The Cambridge Crystallographic Data Centre.
Acknowledgement
The authors gratefully acknowledge financial support from the
National Natural Science Foundation of China for Outstanding
Youth Scholars (grant nos. 21722105), the National Youth
Top-notch Talent Support Program of China, the Key Science and
Technology Innovation Team of Shaanxi Province (2019TD-007,
2019JLZ-02), and the FM&EM International Joint Laboratory of
Northwest University.
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Figure 5 The behavior of H4-3a(Cl)4 and thymine. (a) Fluorescence spectra
of H4-3a(Cl)4 (30 μM) in the presence of increasing concentrations of
thymine at pH = 7.4 (10 mM phosphate buffer) (excitation at 282 nm). (b)
The fluorescence intensity at 390 nm as function of thymine
concentration.
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concentration of thymine (1−20 equiv). Furthermore, a plot of
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Conclusions
In conclusion, we have successfully synthesized the
cyclooctadiene tetraimidazolium compounds H4-L(Cl)4 (L = 3a, 3b)
in
a
rapid and quantitative conversion though
a
metal-carbene-templated photochemical [4+4] cycloaddition in
Chin. J. Chem. 2019, 37, XXX－XXX
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Gan et al.
Report
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Manuscript revised: XXXX, 2019
Manuscript accepted: XXXX, 2019
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Gan et al.
Report
Page No.
Formation of Functional Cyclooctadiene
Derivatives by Supramolecularly-Controlled
Topochemical Reactions and Their Use as Highly
Selective Fluorescent Biomolecule Probes
A
supramolecularly-controlled topochemical reaction in solution provides two
cyclooctadiene-cored tetraimidazolium receptors, which exhibit highly sensitive and selective
fluorescence sensing for thymine relative to other relevant molecules in aqueous solution at
physiological pH (7.4).
Ming-Ming Gan, and Ying-Feng Han*
www.cjc.wiley-vch.de
© 2019 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Chin. J. Chem. 2019, 37, XXX－XXX
This article is protected by copyright. All rights reserved.