Regiospecific [2+2] photocycloadditions of an unsymmetrical olefin in the solid state based on metal-mediated assemblies

Article abstract of DOI:10.1039/c7ce00573c

An unsymmetrical olefin in two coordination polymers underwent solid state [2+2] photocycloaddition reactions resulting in quantitative yields. The reactions afforded the head-to-head and head-to-tail photodimer isomers of cyclobutane derivatives with abs

Full text of DOI:10.1039/c7ce00573c

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DOI: 10.1039/C7CE00573C
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Regiospecific [2+2] photocycloadditions of an unsymmetrical
olefin in the solid state based on metal-mediated assemblies
Jing-Min Chen,a Yi-Xuan Hou,a Qian-Kun Zhou,a Hao Zhang,a and Dong Liu*a
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
www.rsc.org/
An unsymmetrical olefin in two coordination polymers underwent control, owing to its structure demands of close packing in
solid state [2+2] photocycloaddition reactions in quantitative nature.4-9 If the reactive functional groups in adjacent
yields. The reactions afforded the head-to-head and head-to-tail molecules are separated by a long distance in the solid state,
photodimer isomers of cyclobutane derivatives with absolute these groups cannot move freely to suitable orientations for a
regiospecificities.
reaction to occur.4f Furthermore, for an unsymmetrical olefin,
although one of the two photoproducts may be favourably
obtained through the photocycloaddition of a well-designed
solid, the other isomer is not easy to be prepared through tiny
changes of reaction conditions.10 Therefore, the utilization of
crystal engineering to govern the assembly and packing of
organic molecules is of particular importance to control
chemical reactivity and regiospecificity in the solid state.10
The dipyridyl compound trans-1-(3-pyridyl)-2-(4-pyridyl)-
As one of the most important and most frequently used
photochemical reactions for organic synthesis, [2+2]
photocycloaddition has attracted considerable attention.1 This
is because the products that afforded by photochemical [2+2]
cycloaddition reactions are often difficult or impossible to
achieve by conventional organic synthetic methodologies.1
According
to
Schmidt’s
postulate
for
a
[2+2]
photocycloaddition reaction, each pair of olefinic bonds in the
olefin molecules should be aligned parallel with a separation
less than 4.2 Å.2 To this end, many photochemical [2+2]
cycloaddition reactions can be conducted in solutions based on
random molecular collision. However, when the solution-
based [2+2] photocycloaddition reactions are occurred
between two molecules of unsymmetrical olefins, the
reactions usually afford regio- and stereo- isomeric
cyclobutane mixtures.3 Owing to the similar physical and
chemical properties of these isomers, their mixtures are
difficult to be separated and purified. Although the selectivities
can be remarkably enhanced by using suitable templates, such
solution-based reactions are still hard or unable to produce
absolute regiospecific products in quantitative yields.3
ethylene (
adjacent molecules of
the head-to-head or head-to-tail modes with the regulation of
suitable noncovalent interactions. After UV irradiation, the
1
) is an unsymmetrical olefin. Each pair of the
may be aligned to be photoreactive in
1
molecules of
1
with different arrangements would transform
) or 1,3-
), respectively
to 1,2-bis(3-pyridyl)-3,4-bis(4-pyridyl)cyclobutane (
bis(3-pyridyl)-2,4-bis(4-pyridyl)cyclobutane
(Scheme 1).
2
(3
Fortunately, reactions proceeded in the solid state provide
valuable opportunities to generate remarkable regio- or
stereo-specific organic compounds with high yields.4-9
However, the reactivity of a solid-state compound is difficult to
a.Key Laboratory of Energetic Materials of Anhui Province, College of Chemistry and
Materials Science, Huaibei Normal University, 100 DongShan Road, Huaibei
235000, Anhui (P. R. China). E-mail: dongliu@chnu.edu.cn
Scheme 1 Possible [2+2] photocycloadditions based on the head-to-head
and head-to-tail arranged molecules of 1.
† Electronic Supplementary Information (ESI) available: Details of synthesis, details
of crystal structure refinement, selected bond distances and angles, PXRD patterns,
1H NMR spectra, 13C NMR spectra, HRMS spectra, TGA curves, UV-vis absorption
spectra and X-ray crystallographic files in CIF format. CCDC 1522971-1522975. For
ESI and crystallographic data in CIF or other electronic format see DOI: See DOI:
10.1039/x0xx00000x
Compound
on
Heck reaction11 between 3-iodopyridine and 4-
vinylpyridine. To test whether the pure compound is
1 was prepared via a modified procedure based
a
1
photoreactive, single crystals of the olefin were obtained by
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slow evaporation of a saturated MeOH solution within two the dinuclear Ag(I) units good templates to clip the
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DOI: 10.1039/C7CE00573C
1 as neighboring molecules of 1 within relatively short distance. As
days. A perspective view of the packing mode of
determined by single crystal X-ray diffraction is shown in Fig. 1. a consequence of the assembly process, two adjacent olefinic
The molecules of in the crystal lattice are not parallel aligned bonds of within the double chain are parallel to each other
and the distances between the nearest neighbor olefinic bonds with a separation of 3.72 Å (dashed purple lines in Fig. 2),
1
1
are 6.66 or 7.31 Å. Such an arrangement of
Schmidt’s topochemical criteria for a photochemical [2+2] photochemical [2+2] cycloaddition.2
cycloaddition.2 Powder X-ray diffraction (PXRD) pattern, 1H
To evaluate the photoreactivity of 1a
1
does not meet which satisfy the distance criterion for
a
solid state
,
a powdered
NMR, 13C NMR and HRMS spectra indicated the good phase crystalline sample of 1a was exposed to UV irradiation for 6 h.
purity of
1
(Fig. S1-4, ESI†). When a powdered crystalline The irradiation resulted in dimerization of
1
to give
2
in
1
1
sample in this form was exposed to UV irradiation for one day quantitative yield, as evident by H NMR spectroscopy. The H
using a 20 W LED lamp (λem = 365 nm),
1 was confirmed to be NMR spectrum shows complete disappearance of the signals
photostable from 1H NMR spectrum (Fig. S2, ESI†).
for the olefinic protons at 7.57 and 7.41 ppm and the
emergence of a sharp signal at 4.65 ppm due to cyclobutane
protons (Fig. S2, ESI†). In some especially graceful work,
MacGillivray and co-workers have employed
a ditopic
carboxylic acid to hold a pair of photoreactive molecules of
1
in a head-to-head configuration through hydrogen bonding
interactions. Irradiation with light leads to the formation of a
head-to-head photodimer of 1 15a
.
Another photoreactive solid
Fig. 1 View of the packing mode of 1 along the b-axis.
involving
1
is (bta2-)·2(3,4-Hbpe+) (bta
=
1,2,4,5-
In the past decades, dipyridyl compounds have proved
effective for incorporation into coordination assemblies due to
their good coordination abilities.12 Thus, as a dipyridine,
be parallel arranged within short separations for
photoreactions in head-to-head or head-to-tail fashions
through the modification of appropriate coordination bonds.
benzenetetracarboxylic acid).15b Owing to the limitation of its
intrinsic structure, photoreaction of (bta2-)·2(3,4-Hbpe+) could
1 may
only form of
a
mixture of two isomers.15b However,
photoreactive coordination complex containing
reported previously.16
1 has not been
Since the enhancement of the photoreactivity of
1 through
metal-mediated assemblies has not been investigated
previously, we herein report the utilization of metal ions to
tune the orientations of the molecules of
regiocontrolled syntheses of two different photodimer isomers
and . In some particularly elegant work, Biradha and co-
workers have skillfully utilized Ag(I) ions to prepare
photodimer isomers of unsymmetrical olefins in appropriate
conditions.10e,f However, the preparation of two regiospecific
cyclobutane isomers from [2+2] photocycloadditions of an
unsymmetrical olefin via adjusting of different metal ions has
not been investigated until now.
1 for the excellently
2
3
Fig. 2 The ladder-like structure of 1a. All hydrogen atoms and solvent water
molecules are omitted for clarity. The cyan, red and blue balls represent Ag,
O and N atoms, respectively.
In order to determine the structure of the photodimer, the
cyclobutane was isolated through extraction from reacted 1a
using CH2Cl2 and Na2H2edta/NaOH solution. The extraction
afforded
NMR spectroscopy and HRMS (Fig. S2-4, ESI†). X-ray
crystallography further determined the stereochemistry of
crystallizes in the orthorhombic space group Pbca. Each
asymmetric unit contains one molecule of . As shown in Fig.
3, is a head-to-head photodimer based on . PXRD pattern
2 as a colorless powder, which was characterized by
Compound {[Ag2(1,4-ndc)(
the reaction of AgNO3, 1,4-naphthalenedicarboxylic acid (1,4-
H2ndc) and via self-assembly using distilled water as solvent
1)2]·2H2O}n (1a) was obtained by
2. 2
1
under hydrothermal conditions. The purity of 1a was
confirmed by PXRD and 1H NMR spectroscopy (Fig. S1-2, ESI†).
Thermogravimetric analysis (TGA) indicated that 1a is stable up
to 200 °C (Fig. S5, ESI†). Single-crystal analysis revealed that 1a
crystallizes in the triclinic space group Pī. Each asymmetric unit
consists of two Ag(I) ions, one 1,4-ndc2- anion, two molecules
2
2
1
indicated that the single crystal used in the structure
determination was representative of the bulk sample (Fig. S1,
ESI†).
of
1
and two discrete water molecules. In 1a, Ag(I) ions are
to generate a one-dimensional (1D) zigzag chain.
bridged by
1
Each pair of neighboring chains, related by center of
symmetry, are linked by argentophilic forces13,14 to form a
ladder-like structure (Fig. 2). The positive charges of Ag(I) ions
in 1a are balanced by 1,4-ndc2- anions. It is noted that the
molecules of
1 in the double chain are arranged in a head-to-
head fashion and the distances between adjacent Ag(I) ions
are 3.15 and 3.34 Å, respectively. These separations guarantee
Fig. 3 X-ray molecular structure of 2.
2 | J. Name., 2012, 00, 1-4
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The successful isolation of the head-to-head photodimer
encouraged us to obtain the head-to-tail product
2
the steric hindrance of the trinuclear cluster [Cd3(H2O)(COO)4],
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DcOaI:n1n0o.1t039/C7gCeEn00e5r7a3tCe
3
. However, {[Cd3(btre)(1,2,3-btc)2(H2O)3]·3H2O}n
the preparation of head-to-tail photoproducts from interpenetrating architecture. The void space of this complex is
1
unsymmetrical dipyridyl-substituted olefins is a challenge occupied lattice water molecules.17 PXRD pattern and H NMR
because the head-to-tail packing mode of unsymmetrical spectrum confirm the single crystal model is representative of
dipyridine molecules is not easy to predict. Considering the the bulk product (Fig. S1-2, ESI†). According to the TGA curve,
coordination chemistry of common metal ions, we found that 1b is found to be stable up to 355 °C (Fig. S5, ESI†). A closer
the assembly of a mixture of dicarboxylate, dipyridine and view of the four-fold entanglement in 1b indicates that each
Zn(II) salt can provide potential opportunity to generate three- pair of adjacent molecules of
1 in neighboring coordination
dimensional (3D) framework with large cavities.12 To stabilize frameworks is closely aligned in a head-to-tail arrangement.
the architecture, the cavities can be filled by one or more The separation between neighboring olefinic bonds is 3.84 Å
crystallographic equivalent frameworks.12 If the adjacent (dashed purple lines in Fig. 4c). Such a metal-organic directed
frameworks are packed with inversion symmetry, the arrangement of
1 appears to provide appropriate conditions
molecules of unsymmetrical dipyridine in adjacent frameworks for a photoinduced [2+2] cycloaddition.2
may be arranged in a head-to-tail fashion. Therefore, Zn(NO3)2
When a crystalline sample of 1b was subjected to UV
was selected as a starting material to react with 1,4-H2ndc and irradiation for 8 h, 100% conversion of olefinic bonds to
1
. Fortunately, another photoreactive coordination compound cyclobutane rings was observed. The formation of
3 was
{[Zn(1,4-ndc)( )]2·H2O}n (1b) was obtained. confirmed by complete disappearance of the olefinic signals at
1
7.60 and 7.40 ppm and the appearance of a new set of peaks
at 4.72 and 4.65 ppm due to cyclobutane protons (Fig. S2,
ESI†). To confirm the stereochemistry of the photoproduct,
colorless powder of
of 1b. Slow solvent evaporation over a period of two days
produced colorless blocks of . A crystal structure analysis
confirmed the head-to-tail conformation of (Fig. 5).
Compound crystallizes in the monoclinic space group P21/n.
Each asymmetric unit contains one half molecule of . The
purity of was further verified by PXRD, NMR spectroscopy
3 was extracted from the reacted sample
3
3
3
3
3
and HRMS (Fig. S1-4, ESI†).
Fig. 4 (a) The single 3D framework of 1b. All hydrogen atoms and solvent
water molecules are omitted for clarity. The cyan, red and blue balls
Fig. 5 X-ray molecular structure of 2.
represent Zn,
O and N atoms, respectively. (b) Simplified four-fold
As two isomers,
differences. There are eight head-to-head isomeric molecules
in each crystal lattice of . Thus, the space that occupied by
each molecule of
is approximately 486.4 Å3 since its cell
volume is 3891.5 Å3. For , 984.1 Å3 of the cell volume is filled
by two head-to-tail isomeric molecules. Therefore, each
molecule of
should occupy a space of 492.1 Å3. Apart from
the difference between relative arrangements of pyridyl
groups, the shapes of cyclobutane groups in and are also
different. The four carbon atoms of cyclobutane group in is
obviously folded. However, nearly coplanar carbon atoms of
cyclobutane group are existed in
UV-vis absorption spectra of
2 and 3 exhibit distinct structural
interpenetrating architecture of 1b. (c) View of the close contacts of olefinic
bonds between interpenetrating frameworks of 1b.
2
1b crystallizes in the monoclinic space group P21/n. Each
asymmetric unit consists of one Zn(II) ion, one 1,4-ndc2- anion,
one molecule of
1b, each Zn(II) ion is bridged by two 1,4-ndc2- anions to form a
[Zn(1,4-ndc)]n chain extending along the c axis. Meanwhile, the
2
3
1 and one half of lattice water molecule. In
3
[Zn(1,4-ndc)]n chains are linked by the molecules of
a 3D diamondoid framework of [Zn(1,4-ndc)( )]n with 1D
1 to afford
2
3
1
2
channels that run along the b axis (Fig. 4a). The void space of
the single net of 1b is filled by mutual interpenetration of
three crystallographic equivalent networks, forming a four-fold
interpenetrating 3D diamondoid architecture (Fig. 4b). The
topology of 1b is similar with that of {[Cd3(btre)(1,2,3-
btc)2(H2O)3]·3H2O}n (btre = 1,2-bis(1,2,4-triazol-4-yl)ethane;
1,2,3-btc = 1,2,3-benzenetricarboxylate).17 However, owing to
3
.
1-3 indicated that the
maximum absorption peaks of these three organic compounds
are observed at 300, 206 and 207 nm, respectively (Fig. S6,
ESI†). According to the absorbances and concentrations of
these compounds, the molar absorption coefficients of 1-3 can
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be calculated as 6.13 × 104, 5.06 × 104 and 5.05 × 104 L·mol-
1·cm-1, respectively.
and B. F. Abrahams, Angew. Chem., Int. Ed., 2010, 49, 4767;
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Tong, Chem. Commun., 2011, 47, 9384; (d) Y.-C. Ou, D.-S. Zhi,
In summary, we have demonstrated the utilization of metal-
mediated assemblies to prepare suitable templates for solid
state organic syntheses, especially absolutely regiospecific
photochemical [2+2] cycloaddition reactions of an
unsymmetrical olefin. As other reaction conditions of two
systems are the same, the orientations of the olefinic
molecules are mainly determined by the coordination modes
of different metal ions. Work is in progress to expand this
approach to efficiently steer [2+2] photocycloadditions of
other unsymmetrical olefins, with a goal to design excellently
regio- or stereo-specific reactions for applications in organic
synthesis and functional materials.
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Acknowledgements
This work was financially supported by the National Natural
Science Foundation of China (21201068), the Natural Science
Foundation of Anhui Province (1708085MB27), the Key Project
of Natural Science Research for Universities of Anhui Province
(KJ2016A879), the Innovation Team of the Design and
Applications of Advanced Energetic Materials of Anhui Province
and the Innovation and Entrepreneurship Training Program for
Undergraduates of Anhui Province.
8
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Graphic Contents Entry
An unsymmetrical olefin in two coordination polymers undergo solid-state [2+2]
photocycloadditions to afford absolute regiospecific photodimer isomers in quantitative yields.