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Article history:
Received 15 April 2009
Accepted 4 May 2009
Keywords:
Halogen bond
Hydrogen bond
Crystal engineering
Crystallography
Molecular materials
a b s t r a c t
Halogen bonding (XB), as a directional interaction between covalently bound halogen atoms (XB donor)
and Lewis bases (A, XB acceptor), has been recently intensively investigated as a powerful tool in crystal
engineering. After a short review on the origin and general features of halogen bonding, current developments towards (i) the elaboration of three-dimensional networks, (ii) the interaction with anionic XB
acceptors, (iii) its identication in biological systems and (iv) the formation of liquid crystal phases will
be described. Theoretical analyses, statistical studies and experimental electron density determinations
converge to describe halogen bonding as a relatively weak structure directing tool, when compared with
hydrogen bonding. However, when the halogen atom is strongly activated as in iodoperuorinated molecules or cationic aromatic systems can halogen bonding act as an efcient and reliable structure directing tool.
2009 Elsevier Ltd. All rights reserved.
1. Introduction
Halogen bonding describes a directional interaction between
covalently bound halogen atoms (X) and Lewis bases (A). The
halogen atom is typically bonded to a carbon or another halogen.
Halogen atoms themselves can act as Lewis bases in halogen halogen interactions. The strong observed preference for linear
DAX A interaction parallels that known for DAH A hydrogen
bonds (HB) and preferences for the geometries at the acceptor (Lewis base) are also consistent with those observed in hydrogen
bonding. This analogy has led to dene the halogen atom as XB donor, the Lewis base as XB acceptor even if the latter is the electron
density donor in these interactions. While Hassel was one of the
very rst to realize that halogen atoms could form attractive interactions with Lewis bases [1], the following studies concentrated on
adducts of dihalogen molecules with Lewis bases [2]. The role of
chlorochloro interactions reported by Schmidt in crystal engineering [3,4], the preference for two distinct geometries, identied
as type I and type II by Parthasarathy [5] and Jeffrey [6], further
discussions on the geometry and nature of XB by Desiraju [7] are
important landmarks in this domain, soon followed in the last
10 years by the extensive contributions of Resnati and Metrangolo
who highlighted the potential of aliphatic and aromatic iodoperuorocarbons such as CnF2n+1AI or F5C6AI to act as strong XB donor
molecules [8]. Several excellent reviews on halogen bonding are
now available [9], some of them specically dedicated to metal
complexes as XB acceptors [10,11] together with a recent book
on halogen bonding [12]. In the following, we will therefore con* Tel.: +33 23 23 52 43; fax: +33 23 23 67 32.
E-mail address: marc.fourmigue@univ-rennes1.fr
1359-0286/$ - see front matter 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.cossms. 2009.05.001
37
M. Fourmigu / Current Opinion in Solid State and Materials Science 13 (2009) 3645
-
-
X +
X +
-
+
X -
2
+ X
(a)
X +
type II
C interactions
I
F
A (Lewis base)
X
interaction
Scheme 1. Geometrical preferences (i) for the halogen halogen interactions: type
I: h1 h2; type II: h1 90 involving the XB acceptor, h2 180 involving the XB
donor; (ii) for the CAX A interaction where A is a Lewis base and h 180.
C
and
type I
-
C
Br
Br
(b)
F
Me2N
N
hybridization in the following order: CCAI > C@CAI > R3CAI and is
also strongly accentuated in the presence of electron withdrawing
atoms as in iodoperuorocarbons such as F2n+1CnAI or F5C6AI [17].
As a consequence, the type II geometry (Scheme 1) offers two
different roles for the halogen atoms; one of them provides the
Lewis base site situated orthogonal to its CAX bond, and aligned
in a linear arrangement with the r-hole of the other halogen. This
picture is reinforced by the geometry and nature of CAX X0 AC
interactions with X X0 where the heavier halogens are much
more likely to play the XB donor [7].
3. A crystal engineering tool: from 1D chains to 3D
interpenetrated networks, from organic to coordination
chemistry
The remarkable strength and high directionality of halogen bonds
formed by activated iodo- or bromoperuorocarbons has been the
basis for the crystallization of numerous 1D systems, either based
on ditopic XB donor and ditopic XB acceptor (Scheme 2a) or from single molecules bearing both a XB donor and acceptor moieties
(Scheme 2b and c) [19,20]. Note also the recently reported structures
derived from asymmetric porphyrins shown in Scheme 2c [21,22] or
other chain systems (Scheme 2d) obtained as powders through
mechanochemical synthesis [23,24].
This very successful approach has been extended to layered
structures involving tridentate XB donors with tridentate XB
acceptors, planar tetradentate XB donors with tetradentate XB
acceptors, etc. [25]. Of particular note are also the adamantoid
architectures formed from the self assembly of tetrahedral polydentate XB donor or acceptors, as shown beautifully in Fig. 2 for
(c)
Br
F
N
H
N
N
H
N
H
N
H
N
N
I
I
F
(d)
F
F
A'
I
A, A' = O, S, NH
A'
I
I
A'
A
F
F
Most of the recent developments of halogen-bonded supramolecular systems were based on neutral donor (haloperuorocarbons, iodoalkenes, and alkynes, . . .) and acceptor moieties of
38
M. Fourmigu / Current Opinion in Solid State and Materials Science 13 (2009) 3645
Lewis base character such as pyridines, dioxane, tetramethyethylenediamine, . . .), as illustrated above in Part 2. However, because
of the essentially electrostatic nature of the XB interaction, charged
systems, where at least the halogen bond acceptor is anionic, can
be expected to provide much stronger interactions than neutral
assemblies. In that respect, I3, IBr2 or Br3 can be considered as
very strong halogen-bonded systems between the neutral dihalogen and one halide anion. Calculations for the HACCAI F
I
(a)
NO2
O2N
I
(b)
N
O
O
F F
+
TTF
I
FF
F F
S
S
EDT-TTF-I
S
S
S
S
EDT-TTFI2
Scheme 4.
FF
O
N
(c)
I
F4
N
O
O
N
F4
N
O
O
O
+
I
O
N
I
O
F4
F4
M. Fourmigu / Current Opinion in Solid State and Materials Science 13 (2009) 3645
Fig. 4. Halogen bonding in the conducting mixed-valence salt (EDT-TTFI2)2+[(isoq)2Cr(NCS)4] [36], showing the CAI SAC halogen bonds (dotted lines)
involving the sulfur atoms of the N-coordinated thiocyanate anions.
[46]. In these salts, each iodine atom is now engaged in XB interaction (Fig. 5), while each halide anion is surrounded by three iodine
atoms with acute I X I angles (X = Cl, Br), a general feature
among XB halide complexes [47]. The large size of the cations hindered however the formation of honeycomb lattices but afforded
layered systems with a recurrent motif shown in Fig. 5. Working
with the larger I anion as XB acceptor and the smaller SMe3+,
NEt4+, NiPr4+ or PEt4+ cations allowed for the isolation of the
sought-after (6,3) topology with the cations in the centers of the
hexagonal frames (Fig. 5) [48].
A beautiful three-component system where now two different
halide anions act as XB donors in the very same crystal has been recently reported by Yamamoto and Kato [49]. In their earlier works
[50], these authors had described the electrocrystallization of TTF
derivatives in the presence of halide anions and neutral XB donor
molecules such as diiodoacetylene, tetraiodoethylene or 1,4-diuoro-tetraiodobenzene to afford layered conducting materials
characterized by partially oxidized cationic TTF-based layers alternating with halogen bonded two-dimensional anionic lattices
39
Fig. 6. Projection view along c of the unit cell of (EDT-TTF)4BrI2(TIE)5 [49]. The size
of the Br and I anions has been increased. Dotted lines indicate the XB
interactions.
40
M. Fourmigu / Current Opinion in Solid State and Materials Science 13 (2009) 3645
N O
N O
II
N O
I
III
N O
IV
F > derivatives without F; peruoroalkyl > peruoroaromatic; alcohol complexes > iodo complexes. Theoretical calculations show
that the interaction energy of R2NO with the strongest XB donors
such as C3F7AI or C6F5AI is half the values found with the strongest
HB donor molecules such as phenol or C3F7OH, demonstrating that,
at least with this specic acceptor molecule, the HB interaction is
always stronger than the XB one.
The interaction of such stable radicals has also been
investigated by 19F NMR. Indeed, since the uorination of aliphatic
or aromatic iodinated molecules strongly enhances their ability
XB to Lewis bases, 19F NMR is an extremely useful tool to investigate intermolecular interactions such as XB [55,56]. With
iodoperuoroalkanes, the signal of the CF2AI uorine atom(s) geminal to the iodine invariably shows a high-eld shift on XB formation as large as 1020 ppm while in peruoroiodoaromatics, the
uorine atom(s) ortho to the iodine also shows albeit to a lesser
extend a similar high-eld shift. When now radical molecules
such as 2,2,6,6-tetramethyl(piperidin-1-oxyl) (TEMPO) are halogen
bonded to iodoperuoroalkanes, an opposite, much larger paramagnetic downeld shift of the signal of the CF2I uorine atoms
is observed [57], which has been attributed to a transfer of some
of the unpaired spin density from the nitroxidic moiety to the peruorinated chain through the heavy halogen atom. Paramagnetic
19
F NMR appears therefore as a simple, effective and powerful tool
to detect and establish qualitatively the strength of the XB interaction. Theoretical investigations of this strong and specic paramagnetic shift were performed on the model TEMPOIACF3 complex. It
was found that the formation of the XB is accompanied by a significant charge polarization of both molecules, and in particular, of
the most polar resonance structure IV (Scheme 5). The best estimation of the gas-phase binding energy of the complex, obtained at
the MP2/aug-cc-pVTZ level, is about 36, and 29 kJ mol1 in CHCl3.
The origin of the down eld shift has been clearly ascribed to paramagnetic contributions determined by Fermi contact interactions
and to spin transfer from TEMPO to the ICF3 uorine atoms.
Solid state NMR has been also recently used as a new spectroscopic ngerprint to determine precisely the intermolecular N I
distances of microcrystalline halogen-bonded systems [58],
through the analysis of the dipolar interactions between the spins
of the 15N and 127I nuclei, since hetero-nuclear dipolar couplings
provide indeed precise information on inter-nuclear distances.
The one dimensional 15N CP-MAS spectrum of powder sample of
benzyl-bis(4-iodobenzyl)amine revealed two magnetically non
equivalent and crystallographically distinct 15N sites in the unit
cell. The magnitudes of the dipolar 15NA127I couplings correspond
to inter-nuclear distances of 2.7 and 2.9 , in very good agreement
of the known range of N I XB lengths.
Perhaps the most reliable experimental method to quantitatively estimate the strength of halogen bonding in the solid state
is the electron density distribution determined from high resolution X-ray diffraction studies (multipole renements) and analyzed
through the Baders quantum theory of atoms in molecules (AIM)
theory [59]. Applied to these systems, this theoretical analysis
demonstrated [60] that the electron densities at the halogen bond
critical points correlate with the interaction energies, exactly in the
same way shown before on HB [61,62]. When a pairwise interatomic interaction is established, a topological saddle conformation of the electron density distribution q(r) is observed at the
inter-atomic surface, where the electron distribution exhibits a
F4
N
N
(bpe)(C6F4I2)
(dpNO)(C6F4I2)
Br
(bpe)(C6F4Br2)
Br
(dp)(C6F4Br2)
F4
O
F4
N
N
Br
F4
Br
41
M. Fourmigu / Current Opinion in Solid State and Materials Science 13 (2009) 3645
H
O
N
N
O
N
N
N
F
N
N
H
O
F
I
n
H
H
O
n
Scheme 7. Co-existence of XB and HB in the 1:1 iodineiso-nicotinamide and the 1:2 tetrauorodiiodobenzeneiso-nicotinamide complexes [66].
3
Fig. 7. Examples of short X O contacts in a ligandprotein complex and nucleic
acids. (a) The 2.2- structure (PDB ID code 1P5E) of phospho-CDK2/cyclin A in
complex with the inhibitor 4,5,6,7-tetrabromobenzotriazole [77]. The inhibitor is
shown with three bromine halogen bonds to peptide carbonyl oxygen atoms of the
protein. Two interactions (middle) involve the lone pairs of the oxygen atom and
one (right) involves the p system of the C@O group. In addition, one halogen bond to
a water molecule (w) is seen (left). (b) Intramolecular halogen bond identied as
stabilizing a DNA junction (PDB ID code 1P54) in the 1.9- structure of
d(CCAGTACbr5UGG) [78]. (c) View of the packing interactions involving three short
I O contacts in a unique six-stranded DNA structure (PDB ID code 1UE2; 1.4 ) of
the sequence d(Gi5CGAAAGCT) (i5C, 5-iodocytosine) [79]. Reproduced from Ref.
[75] with permission of Proc Natl Acad Sci USA.
42
M. Fourmigu / Current Opinion in Solid State and Materials Science 13 (2009) 3645
preferred out-of-plane
halogen bonding
C
H
N
C
preferred in-plane
hydrogen bonding
(a)
(a)
CnH2n+1O
I
O
H
F
F
N
(b)
CnH2n+1O
N
F
F
I
N
CnH2n+1O
CnH2n+1O
Scheme 10. Bent-core complexes.
(b)
F5
CnH2n+1O
N
FF
CnH2n+1O
I
I
FF
OCnH2n+1
(c)
F
CnH2n+1O
N
N
OCnH2n+1
(d)
F
CnH2n+1O
N
m O
N
OCnH2n+1
Scheme 9. Molecular structures of the dimeric (a) or trimeric (bd) complexes giving rise to thermotropic phases (see text).
M. Fourmigu / Current Opinion in Solid State and Materials Science 13 (2009) 3645
(a)
F
N
n
O
F
(CH2)4
m
O
O
F
(b)
I
F
F
I
N
n
PIPBA
PVPy
43
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