Halogen-bonded and interpenetrated networks through the self-assembly of diiodoperfluoroarene and tetrapyridyl tectons (original) (raw)
Crystal Growth & Design, 2003
The N‚‚‚Br halogen bonding effectively drives the intermolecular recognition between bromoperfluoroalkanes and nitrogen substituted hydrocarbons in the liquid and solid phases. The interaction is strong enough to control the self-assembly of N,N,N′,N′-tetramethyl-p-phenylenediamine and 1,8-dibromoperfluorooctane into a cocrystal that is solid and stable at room temperature in air. The first single-crystal X-ray structure of a complex containing bromomoperfluoroalkanes is reported. One-dimensional infinite chains are formed where the two modules alternate. The low affinity that perfluorocarbon derivatives have for hydrocarbon compounds controls the packing of these chains and leads to the formation of a cocrystal where perfluorocarbon and hydrocarbon layers alternate. Bromoperfluoroalkanes are thus new tectons for the formation of hybrid perfluorocarbon-hydrocarbon crystalline materials.
Perfluorocarbon–hydrocarbon self-assembly
Journal of Fluorine Chemistry, 2002
,N 0 -tetramethyldianilines are well known donor modules tailored to p,p-interaction driven self-assembly processes. When N,N,N 0 ,N 0 -tetramethyl-1,4-phenylenediamine (1a) and bis [4-(N,N-dimethylaminophenyl)]methane (1c) interact with 1,4-diiodotetrauorobenzene , the halogen bonding organises the per¯uorocarbon and hydrocarbon modules into the one dimensional linear networks 3a,c overcoming the low af®nity between the per¯uorocarbon and hydrocarbon modules and their tendency to give p,p stacks. The general effectiveness of N,N,N 0 ,N 0 -tetramethyldianilines as speci®cally tailored telechelic modules in the exo-recognition of dihaloper¯uorocarbons has been demonstrated. q
Journal of Fluorine Chemistry, 2009
The supramolecular organization in six solid assemblies involving iodo-and bromoperfluoroarene derivatives is described. Single crystal X-ray analyses show that the formation of the supramolecular architectures is controlled by I À Á Á ÁBr-Ar F , I À Á Á ÁI-Ar F , Br À Á Á ÁI-Ar F , and Cl À Á Á ÁI-Ar F halogen bondings thus proving the X À Á Á ÁX 0 -Ar F supramolecular synthon, where X can be the same as or different from X 0 , is particularly robust. In five of the described architectures halide anions form two halogen bondings and form infinite chains wherein dihaloperfluoroarenes, which function as bidentate electron acceptors, and halide anions, which function as bidentate electron donors, alternate. This behaviour shows halide anions have a fair tendency to work as bidentate halogen bonding acceptors. ß
Connectivity and Topology Invariance in Self-Assembled and Halogen-Bonded Anionic (6,3)-Networks
Molecules (Basel, Switzerland), 2017
We report here that the halogen bond driven self-assembly of 1,3,5-trifluorotriiodobenzene with tetraethylammonium and -phosphonium bromides affords 1:1 co-crystals, wherein the mutual induced fit of the triiodobenzene derivative and the bromide anions (halogen bond donor and acceptors, respectively) elicits the potential of these two tectons to function as tritopic modules (6,3). Supramolecular anionic networks are present in the two co-crystals wherein the donor and the acceptor alternate at the vertexes of the hexagonal frames and cations are accommodated in the potential empty space encircled by the frames. The change of one component in a self-assembled multi-component co-crystal often results in a change in its supramolecular connectivity and topology. Our systems have the same supramolecular features of corresponding iodide analogues as the metric aspects seem to prevail over other aspects in controlling the self-assembly process.
Collection of Czechoslovak Chemical Communications, 2002
2,2':6',2''-Terpyridine (1) is a well-known electron donor module in metal coordination chemistry and typically works as a tridentate ligand. Here it is shown that 1 can also work as electron donor towards iodoperfluorocarbons both in solution and in the solid phase. Halogen-bonded supramolecular systems are thus obtained. Specifically, terpyridine 1 self-assembles with 1,2,4,5-tetrafluoro-3,6-diiodobenzene (2) and affords the trimeric adduct 3, which is stable and crystalline in the air at room temperature. Single crystal X-ray analysis shows how in adduct 3 both iodine atoms of one molecule of 2 are halogen-bonded to the nitrogen atoms of external pyridine rings of two molecules of 1 that act as monodentate electron donors.
Acta Crystallographica Section C Structural Chemistry, 2017
After reporting the structure of a new polymorph of 1,3,5-trifluoro-2,4,6-triiodobenzene (denoted BzF3I3), C6F3I3, (I), which crystallized in the space group P21/c, we perform a comparative analysis with the already reported P21/n polymorph, (II) [Reddy et al. (2006). Chem. Eur. J. 12, 2222–2234]. In polymorph (II), type-II I...I halogen bonds and I...π interactions connect molecules in such a way that a three-dimensional structure is formed; however, the way in which molecules are connected in polymorph (I), through type-II I...I halogen bonds and π–π interactions, gives rise to an exfoldable lamellar structure, which looks less tightly bound than that of (II). In agreement with this structural observation, both the melting point and the melting enthalpy of (I) are lower than those of (II).
Perfluorocarbon-Hydrocarbon Discrete Intermolecular Aggregates: An Exceptionally Short N⋯I Contact
Supramolecular Chemistry, 2002
1-Iodoperfluoroheptane (1a) and tetramethylethylenediamine (2, TMEDA) form the 2:1 ratio stable aggregate 3a and a similar behaviour is shown by 1-iodoperfluoroalkanes 1b-e and iodopentafluorobenzene 1f. These aggregates have been characterised in solution by 1 H/ 19 F-NMR spectroscopy and in the solid state through IR and single crystal X-ray diffraction. The determined structure of 3a (triclinic, a 5 6.2283(10), b 5 9.250(2), c 5 15.098(3) Å , a 5 81.369(5), b 5 81.397(5), g 5 86.010(5), V 5 849.3(3) A 23 , T 5 175(3) K, space group P-1 (No. 2), Z 5 1; d(calc) 5 2.167 g cm 23 ; 4121 independent reflections, 3665 with I o > 2(I o); final refinement gave R1 5 0.0400, wR2 5 0.0901) showed the second shortest N• • •I interaction found in the crystallographic literature [2.762(3) Å ] and the interdigitation of perfluorocarbon and hydrocarbon modules due to cooperative -C-H• • •F-C-interactions. Calculations to quantify these latter interactions have been also performed.
Advanced Materials, 2002
Comb-shaped polymers greatly differ from branched polymers due to their larger number of side chains. The greater length of these side chains with respect to the polymer cross section grants interesting combinations of properties (for example, the autonomous behavior of the side chains and the ability of the polymer to form layered structures). Liquidcrystalline (LC) polymers [1±3] have a great potential for various functional and high-performance materials and can be conventionally obtained by the covalent incorporation of rigid-rodlike moieties in the side chains. A non-conventional approach to a new class of side-chain LC polymers lies in the use of non-covalent interactions to append the side chains responsible for overall mesomorphicity. Comblike complexes have been obtained by means of various intermolecular interactions such as dipole±dipole and ionic interactions, hydrogen bonding, or charge-transfer interactions. Comb-shaped polymers, such as poly(4-vinylpyridines) and poly(ethyleneimines), have been extensively involved in the formation of comblike complexes through hydrogen-bonding driven selfassembly with long-chain alkyl phenols or carboxylic acids. These complexes have been characterized with various analytical techniques, including microscopy. [5±7] Comb-shaped polymers having perfluorocarbon (PFC) segments in the side chains have recently received interest because of their characteristic structure and properties. Due to their surface behavior [8±10] (including very low surface energies), they have been widely exploited for biomedical applications and for coating engineering. Moreover, their water-and oil-repellent characteristics are especially useful and have been largely exploited in the field of fiber processing. Ran-dom copolymers containing fluorinated segments are much more common than graft copolymers, because of the greater difficulties encountered in the synthesis of a two-phase graft copolymer. [11±13] Beginning from the work by the group of DeSimone, novel perfluorocarbon±hydrocarbon diblock copolymers have been synthesized. Such heterophasic polymeric systems have resulted in a variety of materials with technological promise.