Halogen-Bonding Complexes Based on Bis(iodoethynyl)benzene Units: A New Versatile Route to Supramolecular Materials

González, Lucı́a; Gimeno, Nélida; Tejedor, Rosa M.; Polo, Víctor; Ros, M. Blanca; Uriel, Santiago; Serrano, José Luís

doi:10.1021/cm401849f

Cited by 74 publications

(68 citation statements)

References 57 publications

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“…The field has expanded over the years, as has also been reviewed recently [50]. The majority of halogen-bonded LCs are assembled by combining alkoxystilbazoles, widely used promesogenic molecules [51], with halogen-bond donors such as iodoperfluorobenzenes [52], iodoperfluoroalkanes [53], iodoacetylenes [54], and molecular iodine [55]. From these examples, one could argue that very strong halogen-bond donors are required to stabilize the high-temperature mesophases, and that only molecules containing highly electrophilic iodine atoms are suitable for the task.…”

Section: Photoactive Halogen-bonded Liquid Crystalsmentioning

confidence: 99%

Halogen-Bonded Photoresponsive Materials

Saccone

Cavallo

Metrangolo

et al. 2014

Topics in Current Chemistry

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The aim of the present review is to illustrate to the reader the state of the art on the construction of supramolecular azobenzene-containing materials formed by halogen bonding. These materials include several examples of polymeric, liquid crystalline or crystalline species whose performances are either superior to the corresponding performances of their hydrogen-bonded analogues or simply distinctive of the halogen-bonded species.

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Section: Photoactive Halogen-bonded Liquid Crystalsmentioning

confidence: 99%

Halogen-Bonded Photoresponsive Materials

Saccone

Cavallo

Metrangolo

et al. 2014

Topics in Current Chemistry

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“…26 Alternatively, the intended XB donor can be connected to an sp-hybridized carbon atom which facilitates polarization and leads to an enhanced positive charge. 27,28,29 Only in very rare cases has a combination of approaches been deliberately utilized in order to create an activated XB donor. 30,31 In order to develop a new series of potent XB donors for effective co-crystal synthesis, we decided to combine the electron-withdrawing capabilities of -NO 2 moieties with the polarizing effects of an sp-carbon atom thereby providing a path to highly electrophilic halogen atoms through a 'double-activation' process, Figure 1.…”

Section: Introductionmentioning

confidence: 99%

Crystal Engineering with Iodoethynylnitrobenzenes: A Group of Highly Effective Halogen-Bond Donors

Aakeröy

Wijethunga

Desper

et al. 2015

Crystal Growth & Design

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The benefits of employing a 'double activation' strategy for promoting effective practical cocrystal synthesis through halogen bonding was explored in a systematic supramolecular synthetic study of iodoethynylnitrobenzenes, where the positive electrostatic potential on the iodine atom was enhanced through a combination of an sp-hybridized carbon atom and one or more electronwithdrawing nitro groups. Three model compounds, 1-(iodoethynyl)-4-nitrobenzene (4N-I), 1-(iodoethynyl)-3-nitrobenzene (3N-I) and 1-(iodoethynyl)-3,5-dinitrobenzene (3,5DN-I) were synthesized and characterized, and calculated molecular electrostatic surface potential values on the halogen-bond donor site were about 20-40 kJ/mol higher than those observed for previously well-established halogen-bond donors. The ability of these molecules to drive co-crystal formation was evaluated through a total of 45 co-crystallization experiments with 15 different acceptor molecules. IR spectroscopic data for the resulting products showed that each reaction in the formation of a co-crystal driven by either C-I···N or C-I···O halogen bonds. The analogues bromo-compounds displayed a 60% success rate whereas the chloro-analogues did not yield any co-crystals, emphasizing the importance of the magnitude of the electrostatic aspects of halogen bonding for practical supramolecular synthesis. Ten new crystal structures are presented and the outcome (in terms of stoichiometry and connectivity) is largely predictable. A comparison of I···acceptor distances found in these structures with relevant data from the CSD shows that iodoethynylnitrobenzenes consistently give rise to a larger reduction of combined van der Waals radii (for C-X···acceptor) than do other well-known halogen bond donor moieties.

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“…Gonzalez et al. reported on halogen‐bonded complexes using bis(iodoethynyl)benzene isomers and pyridine derivatives (Scheme ) . The linear trimeric halogen‐bonded complexes derived from 1,4‐bis(iodoethynyl)benzene show smectic B and crystal G mesophases (Figure ).…”

Section: Halogen‐bonded Liquid Crystalsmentioning

confidence: 99%

“…reportedo nh alogen-bonded complexes using bis(iodoethynyl)benzene isomers and pyridine derivatives (Scheme 10). [80] The linear trimeric halogen-bonded complexes derived from 1,4-bis(iodoethynyl)benzenes how smectic Ba nd crystal Gm esophases (Figure 7). The bent shaped complexes derived from 1,3-bis(iodoethynyl)benzenee xhibited SmAP-like liquid crystal phases, in whcih "P" stands for polar.I t was observed that the mesophase behaviors in thesec omplexes are dependent on the number of aromatic rings present.…”

Section: Scheme6chemical Structures Of Trimeric Halogen-bonded Complmentioning

confidence: 99%

The Halogen Bond: An Emerging Supramolecular Tool in the Design of Functional Mesomorphic Materials

Wang

Bisoyi

Urbas

et al. 2018

Chemistry A European J

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Owing to their dynamic attributes, non-covalent supramolecular interactions have enabled a new paradigm in the design and fabrication of multifunctional material systems with programmable properties, performances, and reconfigurable traits. Recently, the "halogen bond" has become an enticing supramolecular synthetic tool that displays a plethora of promising and advantageous characteristics. Consequently, this versatile and dynamic non-covalent interaction has been extensively harnessed in various fields such as crystal engineering, self-assembly, materials science, polymer chemistry, biochemistry, medicinal chemistry and nanotechnology. In recent years, halogen bonding has emerged as a tunable supramolecular synthetic tool in the design of functional liquid-crystalline materials with adjustable phases and properties. In this Concept article, the use of halogen bond in the field of stimuli-responsive smart soft materials, that is, liquid crystals is discussed. The design, synthesis and characterization of molecular and macromolecular liquid crystalline materials are described and the modulation of their properties has been emphasized. The power of halogen bonding in offering a large variety of functional liquid crystalline materials from readily accessible mesomorphic and non-mesomorphic complementary building blocks is highlighted. The article concludes with a perspective on the challenges and opportunities in this emerging endeavor towards the realization of enabling and elegant dynamic functional materials.

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Halogen-Bonding Complexes Based on Bis(iodoethynyl)benzene Units: A New Versatile Route to Supramolecular Materials

Cited by 74 publications

References 57 publications

Halogen-Bonded Photoresponsive Materials

Halogen-Bonded Photoresponsive Materials

Crystal Engineering with Iodoethynylnitrobenzenes: A Group of Highly Effective Halogen-Bond Donors

The Halogen Bond: An Emerging Supramolecular Tool in the Design of Functional Mesomorphic Materials

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