Solid state synthesis under supramolecular control of a 2D heterotetratopic self-complementary tecton tailored to halogen bonding

Abstract

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Halogen Bonding in Supramolecular Chemistry

“…For example, 4,4′‐bipyridine, and its ethylene analogue 4,4′‐ethane‐1,2‐diyldipyridine, afford linear chains with 1,4‐diiodotetrafluorobenzene, but zigzag chains on interaction with the 1,3‐ and 1,2‐ analogues (Figure 2). 43 Many cases have been described where the XB donor,24c, 43c the XB acceptor,9a, 25b, 36, 38, 44 or both sites23f, 35c present an angled geometry. The linear and/or angled modules can be both neutral and anionic species, and halide anions frequently function as bidentate XB acceptors and assume linear or angled geometries17b, 26b, 45 as a function of the overall crystal‐packing requirements.…”

Ab initio calculations on halogen‐bonded complexes and comparison with density functional methods

“…Indeed, most of the energetic and structural features found in hydrogen‐bonded complexes are reproduced in halogen‐bonded complexes as well. Owing to its strength, selectivity, and directivity, halogen bonding has led to a number of applications in fields, as diverse as molecular recognition, enantiomers's separation, crystal engineering, and supramolecular architectures 2–28. In particular, the utilization of this specific interaction in the context of drug design is nowadays coming to light clearly 3, 29–35.…”

Tuning second-order NLO responses through halogen bonding

“…1 Halogen bonding (XB), 2 any noncovalent interaction involving halogens as electrophilic sites, is a rather new item in the supramolecular toolbox and shares numerous properties with the better known HB. 5 Before studying the electrooptical activities of the halogen-bonded 2D films that these modules form, we decided to evaluate their NLO properties at the molecular level. 3 Keen to extend the use of XB to the self-assembly of organic thin films for nonlinear optical (NLO) and optoelectronic applications, 4 we have synthesized the XB-based selfcomplementary tectons N,N-dimethyl-4-[(E)-2-(2,3,5,6-tetrafluoro-4-iodophenyl)vinyl]aniline (1a) and N,N-dimethyl-4-[(1E,3E)-4-(2,3,5,6-tetrafluoro-4-iodophenyl)buta-1,3-dien-1-yl]aniline (1b) (Scheme 1).…”