Activating Chalcogen Bonding (ChB) in Alkylseleno/Alkyltelluroacetylenes toward Chalcogen Bonding Directionality Control

Article abstract of DOI:10.1002/anie.202011981

Activation of a deep electron-deficient area on chalcogen atoms (Ch=Se, Te) is demonstrated in alkynyl chalcogen derivatives, in the prolongation of the (C≡)C?Ch bond. The solid-state structures of 1,4-bis(methylselenoethynyl)perfluorobenzene (1Se) show the formation of recurrent chalcogen-bonded (ChB) motifs. Association of 1Se and the tellurium analogue 1Te with 4,4′-bipyridine and with the stronger Lewis base 1,4-di(4-pyridyl)piperazine gives 1:1 co-crystals with 1D extended structures linked by short and directional ChB interactions, comparable to those observed with the corresponding halogen bond (XB) donor, 1,4-bis(iodoethynyl)-perfluorobenzene. This “alkynyl” approach for chalcogen activation provides the crystal-engineering community with efficient, and neutral ChB donors for the elaboration of supramolecular 1D (and potentially 2D or 3D) architectures, with a degree of strength and predictability comparable to that of halogen bonding in iodoacetylene derivatives.

Full text of DOI:10.1002/anie.202011981

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Accepted Article
Title: Activating chalcogen bonding (ChB) in alkylseleno/
alkyltelluroacetylenes toward ChB directionality control
Authors: Marc Fourmigue, Arun Dhaka, Olivier Jeannin, Ie-Rang Jeon,
Emmanuel Aubert, and Enrique Espinosa
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To be cited as: Angew. Chem. Int. Ed. 10.1002/anie.202011981
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10.1002/anie.202011981
Activating chalcogen bonding (ChB) in alkylseleno/ alkyltelluroacetylenes
toward ChB directionality control
Arun Dhaka, Olivier Jeannin, Ie-Rang Jeon, Emmanuel Aubert, Enrique Espinosa and Marc
Fourmigué*
[*
] A. Dhaka, Dr. O. Jeannin, Dr. I.-R. Jeon, Dr. M. Fourmigué
Univ Rennes, CNRS, ISCR (Institut des Sciences Chimiques de Rennes) UMR 6226,
3
5042 Rennes, France.
E-mail: marc.fourmigue@univ-rennes1.fr
Dr. E. Aubert, Pr. E. Espinosa
Laboratoire CRM2, UMR CNRS 7036, Institut Jean Barriol, Université de Lorraine, BP
7
0239, 54506 Vandoeuvre-les-Nancy, France
ABSTRACT
Activation of a deep electron-deficient area on chalcogen atoms (Ch = Se, Te) is demonstrated
here in alkynyl chalcogen derivatives, in the prolongation of the (C≡)C−Ch bond. The solid-
state structures of 1,4-bis(methylselenoethynyl)perfluorobenzene (1Se) show the formation of
recurrent chalcogen-bonded (ChB) motifs. Association of 1Se and the tellurium analog 1Te
with 4,4’-bipyridine and with the stronger Lewis base 1,4-di(4-pyridyl)piperazine gives 1:1 co-
crystals with 1D extended structures linked by short and directional ChB interactions,
comparable to those observed with the corresponding halogen bond (XB) donor, 1,4-
bis(iodoethynyl)-perfluorobenzene. This “alkynyl” approach for chalcogen activation provides
the crystal engineering community with efficient, and neutral ChB donors for the elaboration
of supramolecular 1D (and potentially 2D or 3D) architectures, with a degree of strength and
predictability comparable to that of halogen bonding in iodoacetylene derivatives.
1
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Angewandte Chemie International Edition
10.1002/anie.202011981
Introduction
Crystal engineering strategies are rooted in our ability to manipulate intermolecular interactions
with a high degree of prediction about the expected outcome of the attempted intermolecular
associations.[1] This predictability is not only a direct consequence of the strength of the
interaction, but also of its directionality.[2,3] Besides hydrogen bonding,[4,5] the so-called sigma-
hole interactions have raised in the last 20 years a very strong interest. For example, the success
[
6]
[7,8,9]
of halogen bonding and its applications in a wide variety of domains,
is essentially based
not only on its strength, but also on its strong directionality as the charge-depleted area which
develops in the prolongation of a C−X bond is concentrated within a limited area.
Besides halogen bonding, chalcogen bonding also enters in this category of sigma-hole
interactions.[10] First investigated by theoretical methods,[11,12,13] and on the basis of high-
resolution diffraction studies,[14,15] ChB has been known and identified for decades in the crystal
structures of many chalcogenated derivatives,[16,17] but its involvement in crystal engineering
strategies still struggles to make a strong mark as its XB analog, due mainly to a lack of control
of directionality. Indeed, at variance with halogens, the presence of two σ-bonds on the divalent
chalcogen atom generates two σ-holes. Different strategies have been reported recently
however, aiming at controlling in some way the ChB interactions for a specific goal. We can
mention first the association on the same molecule of strong ChB donor and acceptor sites, as
in 1,2,5-telluradiazoles,[18] 1,2-chalcogenazole N-oxide,[19,20], benzo-1,3-chalcogenazole,[21]
favoring the formation of infinite ribbons[18,22] or discrete supramolecular assemblies.[23] The
use of ChB donors in organocatalysis[24,25] or anion recognition[26,27] processes involves the
preparation of bidentate chelating molecules bearing two activated chalcogen atoms, able to
interact with one single Lewis base, neutral or anionic, as found in molecules linking two
tellurophenes,[28] two 5-(methylchalcogeno)-1,2,3-triazole moieties,[29] two thiophene units
bearing Electron Withdrawing Groups (EWG),[30] or two selenocyanate groups.[31] In several
examples, one of the two substituents linked to the chalcogen atom has a strong EWG character,
favoring the formation of a stronger σ-hole in the prolongation of this EWG−Ch bond. This
strategy to recover part of the directionality characteristic of XB has been explored with para-
bis(selenocyanatomethyl)benzene (Scheme 1a), which co-crystallizes with 4,4’-bipyridine to
form a ChB chain motif through very short and directional Se•••N≡C contacts.[32] This 1D
structure mimics those obtained with ditopic XB donors such as 1,4-diiodoperfluorobenzene
(Scheme 1b), or diiodoacetylene. Looking for more rigid ditopic ChB donors than these
selenocyanate derivatives, we considered the possibility to replace the two iodine atoms in rigid
2
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Angewandte Chemie International Edition
10.1002/anie.202011981
ditopic XB donors by selenoalkyl or telluroalkyl moieties (Scheme 1c) and we specifically
concentrated here on the 1Se and 1Te derivatives, as analogs of 1,4-
bis(iodoethynyl)perfluorobenzene 2, with the idea that an alkynyl group could activate a strong
σ-hole on the chalcogen atom as it does on iodine.
Scheme 1.
Several linear oligoalkynes, α,ω-substituted with chalcogenomethyl groups,
MeCh−(C≡C)
n
−ChMe (Ch = Se, Te; n = 2-4), were described in 2002.[33,34] Among them, one
(Ch = Te, n = 2) was shown to organize into tubular nanostructure stabilized by Ch•••Ch
intermolecular interactions slightly below the van der Waals contact distance,[35] but their
potential to form co-crystals with Lewis bases through ChB interactions had not been addressed.
To answer this question, we investigated the ability of 1Se or 1Te to co-crystallize with linear,
ditopic Lewis bases such as the prototypical 4,4’-bipyridine. The success of this approach, as
shown below, provides us with extremely efficient and directional ChB donors for the
elaboration of supramolecular architectures, with a degree of strength and predictability
comparable to that of halogen bonding.
The ChB donor ability of 1Se and 1Te has been first evaluated from the calculated
values of the extrema of the electrostatic potential surfaces (ESP), the largest the positive ESP
value, the more important the
σ
-hole at the chalcogen atom and therefore the ChB donor ability.
3
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Angewandte Chemie International Edition
10.1002/anie.202011981
As shown in Fig. 1 (see calculation details in ESI), both Se and Te derivatives exhibit a notable
σ-hole in the prolongation of the (C≡)C−Ch bond, much stronger than that in the prolongation
of the other H C−Ch bond (Fig. S1 in ESI). This points already for a potential good
3
directionality of ChB interactions involving these atoms. Comparison with the analogous iodo
derivative 2 shows that, albeit slightly smaller (−12%), 1Te exhibits a comparable σ-hole
extremum.
Fig. 1. Details of the ESP maps of (from left to right) 1Se, 1Te and 2 at optimized geometries,
3
plotted on the 0.002 electron/bohr isosurface of the electronic density. The extrema values
Vs,max of the electropositive (blue) area are indicated. Potential scale ranges from 0 (red) to 37.7
(blue) kcal/mol.
The preparation of 1Se (Scheme 2) is based on the metalation of the bis(alkynyl) derivative 4
with BuLi, followed by reaction with grey selenium and alkylation with MeI. This procedure
failed in our hands with tellurium. An alternative route to 1Te involves the reaction of the
bis(alkynylsilver) derivative 5 with methyltelluroniumbromide MeTe−Br.[29c] The diiodo
derivative 2 was prepared as reported earlier from the reaction of the bis(trimethylsilylalkynyl)
compound 3, through reaction with NIS and AgNO
.[36]
3
4
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Angewandte Chemie International Edition
10.1002/anie.202011981
F
F
F
F
F
F
F
H
TMS
Pd catalyst, CuI
I
I
TMS
TMS
NEt , 65°C
3
80%
3
F
F
AgNO /NIS
acetone/
THF
3
F
F
I
I
2
F
K2CO3
AgF/MeOH
F
tBuOH/MeOH
F
F
F
F
H
H
Ag
Ag
4
F
F
5
F
Te
Te
Br /THF
i BuLi, Se, -78°C
ii MeI
2
MeTe-Br
F
F
F
F
F
Se
Se
Te
Te
F
F
F
1
Se
1Te
Scheme 2. Synthetic paths to the 1Se, 1Te and 2.
Compound 2 crystallizes in the monoclinic system (SG P2
1
/c) into layers driven by π−π
interactions (Fig. S2) with the shortest I•••I contacts above 4.05 Å, excluding the presence of
XB interactions. Two polymorphs of 1Se were isolated under different crystallization
conditions (see ESI). Phase A (monoclinic, SG P2 /c) shows inversion-centered Se•••Se
1
contacts (Fig S3) at 3.59 and 3.62 Å i.e. a reduction ratio RR (defined as the actual interatomic
distance over the sum of the van der Waals radii) around 0.95. They correspond to Type I
Ch•••Ch interactions, by analogy with the Type I/Type II terminology adopted for
halogen•••halogen interactions (See Scheme 3).[37] Phase B (tetragonal, SG I4
characterized by 10 independent 1Se molecules, including two 1Se molecules inserted inside
channels (see below) with a refined 2/3 occupancy Molecules are organized through highly
/a) is
1
.
directional Type II Se•••Se contacts(Fig. 2) with facing electrophilic•••nucleophilic regions to
generate tetrahedral motifs, with Se•••Se distances in a 3.63-3.66 Å range (RR = 0.96) (see also
Fig. S4 and Table S2).
5
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Angewandte Chemie International Edition
10.1002/anie.202011981
Scheme 3. Comparison of X•••X and Ch•••Ch interaction motifs. Type II interactions refer to
the so-called halogen bonding (XB) or chalcogen bonding (ChB).
Fig. 2. One tetrahedral motif formed by directional, Type II (C≡)C−Se•••Se ChB in 1Se
(phase B) (See Table S2 and Fig. S4).
These motifs stack along the c-axis to delineate a tubular square-lattice network (Fig. 3a, Fig.
S5) organized into helical chains running along c (Fig. 3b). At the center of these helical stacks,
a large volume is occupied by two other molecules (in red and black in Fig. 3) interacting with
each other within the channels into a double helix through Type I, slightly shorter (RR = 0.92)
Se•••Se interactions (Fig. 3b, Fig. S7, Table S2).
6
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Angewandte Chemie International Edition
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Fig. 3. Detail of the solid-state arrangement in 1Se (Phase B) showing the helical organization
of molecules (only one helix out of six is shown in green, see Fig. S7 for all helices), and two
other molecules inserted inside channels (in red and black).
With these two new 1Se and 1Te derivatives at hand, we can now evaluate their ability
to act as ChB donors in supramolecular assemblies as well-known iodoacetylene derivatives
(
as 2) do with halogen bonding. As shown in Figure 5a, we found that cocrystallization of 2
with bipy leads indeed to the formation of chains with a short and directional I•••N contact (RR
0.79). Using the ditopic ChB donors 1Se and 1Te leads to a very similar 1D motif, with the
=
formation of 1Se•bipy and 1Te•bipy co-crystals which exhibit the sought-after, short and
directional ChB interactions (Table 1), demonstrating the efficiency of the alkynyl substituent
to activate chalcogen atoms toward ChB interactions, with a strength almost comparable to that
of the iodinated analog 2. In both co-crystals, the ChB interaction involves the σ-hole in the
prolongation of the alkynyl−chalcogen bond and the reduction ratio is almost comparable
between iodine (0.79) and tellurium (0.82). In other words, alkynyl-tellurium derivatives can
be as efficient as prototypical alkynyl-iodine derivatives to enter into strong and directional σ-
hole interactions toward Lewis bases.
Figure 5. Details of the solid-state structures of the 1:1 co-crystals of bipy with 2 (a), 1Se (b)
and 1Te (c) (see also Fig. S8).
7
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Table 1. Pertinent structural characteristics of the ChB (XB) interactions in co-crystals (Ch =
Se, Te; X = I).
Co-crystal
Ch/X•••N dist. (Å) RR
C−(Ch/X)•••N angle (°)
173.5(1)
2
1
1
•bipy
2.778(4)
3.055(4)
2.952(4)
0.79
0.89
0.82
Se•bipy
Te•bipy
176.1(1)
173.9(1)
2
•bipy-pip
2.718(9)
0.77
0.76
0.87
0.79
176.9(1)
178.9(1)
171.6(1)
171.8(1)
2
.700(8)
1
1
Se•bipy-pip
Te•bipy-pip
2.995(11)
2.855(4)
In order to further strengthen these ChB interactions, we considered bipyridine analogs which
could exhibit a stronger Lewis base character, as for example observed when one replaces
pyridine with the more electro-rich 4-dimethylaminopyridine (DMAP). To reach this goal, we
envisioned the piperazine derivative[38] hereafter abbreviated as bipy-pip (Scheme 3) which
combines the ditopic character of 4,4’-bipyridine with the stronger Lewis-base character of
DMAP. To our surprise, this interesting molecule has never been used as XB (nor ChB)
acceptor.[39]
Scheme 3. Combining the electron donating effect of −NMe with the ditopic character of
2
bipyridine.
Its co-crystallization with 1Se and 1Te (and 2) was as successful as with bipy and the three 1:1
co-crystals were isolated and structurally characterized. They all exhibit short and directional
σ-hole interactions, in the prolongation of the alkynyl−chalcogen bond, notably shorter than
with bipy itself (see Table 1), with RR value down to 0.79 in 1Te•bipy-pip, and leading to the
recurrent formation of 1D structures (Fig. 6).
8
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Angewandte Chemie International Edition
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Figure 6. Details of the solid-state structures of the 1:1 co-crystals of bipy-pip with 2 (a), 1Se
b) and 1Te (c).
(
In conclusion, we have demonstrated here that an alkynyl moiety can activate a deep electron-
deficient area on chalcogen atoms (Se, Te) in the prolongation of the (C≡)C−Ch bond. The
solid-state structures of 1Se itself highlight the formation of either Type I Ch•••Ch or type II
ChB interactions, with tetrahedral Se
4
motifs leading to a helical structure, which
accommodates extra 1Se molecules within the pores. Association of 1Se and 1Te with ditopic
Lewis bases such as bipy and bipy-pip gives 1:1 co-crystals with 1D structures linked by short
and directional ChB interactions, comparable to those observed in iodoacetylene derivatives.
The success of this “alkynyl” approach provides the crystal engineering community with
efficient, and neutral, ChB donors for the elaboration of supramolecular 1D (and potentially 2D
or 3D) architectures, with a degree of strength and predictability comparable to that of halogen
bonding.
Acknowledgements
This work has been supported by ANR (Paris) as ANR-17-CE07-0025-01 (Nancy) and ANR-
1
7-CE07-0025-02 (Rennes). The EXPLOR mesocentre is thanked for computing facilities
(Project 2019CPMXX0984).
Keywords: Alkynes • Chalcogens • Crystal Engineering • Lewis bases
9
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Angewandte Chemie International Edition
10.1002/anie.202011981
For Table of Content
Chalcogen bond activation by alkynyl substitution is realized in bis(selenomethyl-alkynyl)
and bis(telluromethyl-alkynyl) derivatives, as evidenced in co-crystals with ditopic Lewis
bases such as 4,4’-bipyridine and 1,4-di(pyridin-4-yl)piperazine, with Te•••N interactions as
short as I•••N halogen bonds with analogous iodo-alkynyl derivatives.
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