Please do not adjust margins
New Journal of Chemistry
Page 4 of 6
DOI: 10.1039/C8NJ00962G
COMMUNICATION
Journal Name
well as pyridine as reference) in solution by 19F-NMR titration
experiments. Toluene as solvent represented the best
compromise between a non-competing environment and
sufficient solubility of all species.
Notes and References
1
2
3
a) G. Cavallo, P. Metrangolo, R. Milani, T. Pilati, A. Priimagi,
G. Resnati and G. Terraneo, Chem. Rev., 2016, 116, 2478; b)
L.C. Gilday, S.W. Robinson, T.A. Barendt, M.J. Langton, B.R.
Mullaney and P.D. Beer, Chem. Rev., 2015, 115, 7118.
a) G. Resnati, E. Boldyreva, P. Bombicz and M. Kawano,
IUCrJ, 2015, 2, 675; b) L. Brammer, G. Minguez Espallargas
and S. Libri, CrystEngComm, 2008, 10, 1712; c) K. Rissanen,
CrystEngComm, 2008, 10, 1107.
a) K. Raatikainen, G. Cavallo, P. Metrangolo, G. Resnati, K.
Rissanen, and G. Terraneo, Cryst. Growth Des., 2013, 13
,
871; b) L.C. Gilday and P.D. Beer, Chem. Eur. J., 2014, 20
8379; c) E.A.L. Gillis, M. Demireva, M.G. Sarwar, M.G.
Chudzinski, M.S. Taylor, E.R. Williams and T.D. Fridgen,
Phys. Chem. Chem. Phys., 2013, 15, 7638.
,
4
5
D. Bulfield and S.M. Huber, Chem. Eur. J., 2016, 22, 14434.
E. Dimitrijevic, O. Kvak and M.S. Taylor, Chem. Commun.,
2010, 46, 9025.
6
a) A. Caballero, N.G. White and P.D. Beer, Angew. Chem. Int.
Ed., 2011, 50, 1845; b) L.C. Gilday, N.G. White and P.D. Beer,
Dalton Trans., 2013, 42, 15766.
Scheme 1: Synthesis of one-sided analogues m-7 and p-7; i)
Pd2dba3 (5 mol%), S-Phos (30 mol%), Boronic ester (6.6 eq), 1,3-
diiodotetrafluorobenzene (1 eq), K2CO3 (2 eq); ii) HOTf (200 eq),
N-iodosuccinimide (4 eq).
7
8
D. Cao, M. Hong, A.K. Blackburn, Z. Liu, J.M. Holcroft and
J.F. Stoddart, Chem. Sci., 2014, 5, 4242.
a) S.M. Oburn, N.P. Bowling and E. Bosch, Cryst. Growth
Des., 2015, 15, 1112; b) Y. Takeda, K. Hatanaka, T. Nishida
and S. Minakata, Chem. Eur. J., 2016, 22, 10360.
L. Maugeri, J. Asencio-Hernandez, T. Lebl, D.B. Cordes,
A.M.Z. Slawin, M.-A. Delsuc and D. Philp, Chem. Sci., 2016,
7
Titration of syn-m-7 or syn-p-7 with 4a in this solvent resulted
in binding constants of K = 2 M-1 and K = 1 M-1, respectively.
This rather weak coordination is in line with the DFT
computations mentioned above. Various attempts to obtain
9
, 6422.
10 L. Maugeri, E.M.G. Jamieson, D.B. Cordes, A.M.Z. Slawin and
D. Philp, Chem. Sci., 2017, , 938.
11 L. Maugeri, T. Lébl, D.B. Cordes, A.M.Z. Slawin and D. Philp,
J. Org. Chem., 2017, 82, 1986.
12 a) L.-Y. You, S.-G. Chen, X. Zhao, Y. Liu, W.-X. Lan, Y. Zhang,
H.-J. Lu, C.-Y. Cao and Z.-T. Li, Angew. Chem. Int. Ed., 2012,
51, 1657; b) C. J. Massena, A. M. S. Riel, G. F. Neuhaus, D. A.
8
binding data with
5 failed due to precipitation of the Lewis
base or very weak binding. The binding constants of syn-m-7
and syn-p-7 with pyridine as single-point binding reference
compound were only marginally lower (K = 0.9 M-1 and 0.8 M-
1), which casts severe doubt on whether the oxadiazole is
actually bound in a two-point fashion in solution.
Decato and O. B. Berryman, Chem. Commun., 2015, 51
,
1417.
13 C.B. Aakeroy, A. Rajbanshi, P. Metrangolo, G. Resnati, M.F.
Parisi, J. Desper and T. Pilati, CrystEngComm, 2012, 14
6366.
,
Conclusions
14 O. Dumele, N. Trapp and F. Diederich, Angew. Chem. Int.
Ed., 2015, 54, 12339.
15 a) A. Vanderkooy and M.S. Taylor, J. Am. Chem. Soc., 2015,
137, 5080; b) A. Vanderkooy, P. Pfefferkorn and M.S. Taylor,
Macromolecules, 2017, 50, 3807; c) A. Vanderkooy and M.S.
Taylor, Faraday Discuss., 2017, 203, 285.
This study investigated the use of neutral, terphenyl-based
halogen bond donors in two-point recognition. Potential
twofold Lewis basic substrates were screened via DFT
calculations, and oxadiazole as well as pyridazole core motifs
were identified as suitable binding partners, even though gas-
phase binding energies indicated weak coordination.
Crystallographic studies provided clear evidence of two-point
halogen bonding in the solid state between halogen bond
donor m-1 and an oxadiazole derivative. Titration experiments
in solution, however, indicated that the binding is likely too
weak to be exploited in solution-phase applications.
16 S.H. Jungbauer, D. Bulfield, F. Kniep, C.W. Lehmann, E.
Herdtweck and S.M. Huber, J. Am. Chem. Soc., 2014, 136
16740.
17 F. Kniep, S.H. Jungbauer, Q. Zhang, S.M. Walter, S.
Schindler, I. Schnapperelle, E. Herdtweck and S.M. Huber,
Angew. Chem. Int. Ed., 2013, 52, 7028.
18 Y. Zhao and D.G. Truhlar, Theor. Chem. Acc., 2008, 120, 215.
19 S. Grimme, J. Antony, S. Ehrlich and H. Krieg, J. Chem. Phys.,
2010, 132, 154104.
,
S.M.H., J.S. and D.B. thank the Fonds der Chemischen Industrie
and the Deutsche Forschungsgemeinschaft (Cluster of
Excellence RESOLV, EXC 1069) for financial support. C.J. thanks
the project FONDECYT 1150747. J.P. and C.R.P. thank the
MINECO-Spain for the project MAT2014-57465-R.
20 F. Weigend and R. Ahlrichs, Phys. Chem. Chem. Phys., 2005,
7
21 A. Bondi, J. Phys. Chem., 1964, 68, 441.
, 3297.
22 C.Y. Legault; CYLview.1.0b; Université de Sherbrooke; 2009
;
23 P.I. Hidalgo, S. Leal, C.A. Jimenez, E. Vohringer-Martinez, B.
Herrera, J. Pasan, C. Ruiz-Perez and D.W. Bruce,
CrystEngComm, 2016, 18, 42.
Conflicts of interest
24 S.H. Jungbauer, S. Schindler, E. Herdtweck, S. Keller and
S.M. Huber, Chem. Eur. J., 2015, 21, 13625.
There are no conflicts to declare.
4 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins