Halogen-bonded and interpenetrated networks through the self-assembly of diiodoperfluoroarene and tetrapyridyl tectons (original) (raw)
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Journal of Fluorine Chemistry, 2010
The single crystal structures of five co-crystals formed by the reaction of different iodide and bromide salts with di-and triiodoperfluorobenzenes (I-ArF) are reported. All of these perfluorocarbonhydrocarbon systems are heteromeric three-component systems, wherein the weakly coordinating cations favour the formation of naked halides, which function as electron-donors towards the I-ArF modules. The analysis of the crystal structures shows that I À Á Á ÁI-ArF, and Br À Á Á ÁI-ArF halogen bonds (XBs) control the self-assembly of the obtained supramolecular architectures. 2D and 3D supramolecular networks have been obtained, wherein naked iodide and bromide anions act as tri-, tetra-, or pentadentate nodes. The selected examples demonstrate that I-ArF modules can be particularly robust and reliable tectons for XB-based coordination of halide ions and afford supramolecular architectures in a rational and predictable way.
Journal of Molecular Structure, 2005
4,4 0 -bis(dimethylamino)-benzophenone (1) is shown to self-assemble in the solid phase with 1,4-diiodo-tetrafluoro-benzene (TFDIB) to form the air stable compound 1 TFDIB. Single crystal X-ray analysis of this compound reveals a structure consisting of ribbon-like polymeric chains of alternating donor and acceptor molecules. The directing non-covalent halogen bond is characterised by a relatively long O/I distance of 3.097 Å and an O/I-C angle of 163.298. These bond characteristics are due to the coordination of each carbonyl oxygen with two iodine atoms, resulting in a 'zigzag' geometry of the chains. Carbonyl derivatives can thus be considered as new tectons for the formation of hybrid perfluorocarbon-hydrocarbon crystalline materials. q
Studia Universitatis Babes-bolyai Chemia, 2022
A spectacular 2D Halogen Bond Organic Framework (XBOF) was prepared by the mechanochemical solvent-drop grinding method (SCD) starting from 2,7-dipyridylfluorene and 1,3,5-trifluoro-2,4,6-triiodobenzene tectons. The formation of the supramolecular assembly was proved by powder X-ray diffraction measurements and the structural details were collected from the single crystal X-ray diffraction investigations.
Tetrahedron, 2000
AbstractÐThe formation of in®nite 1D networks where diiodoper¯uorocarbons are halogen bonded to di-nitrogen substituted hydrocarbons is described. The N´´´I non-covalent interaction is speci®c, directional, and strong enough to effectively overcome the low af®nity between per¯uorocarbon and hydrocarbon modules and to drive their self-assembly in the solid and liquid phase. Several analytical techniques are used to identify and characterise the electron donation from nitrogen to iodine atoms. The effectiveness of the interaction is largely independent from the overall structure of the involved modules. Indeed, supramolecular architectures have been obtained starting from diiodoper¯uoroalkanes and -arenes (electron poor motifs) as well as from pyridine derivatives and di-or trialkylamines (electron rich motifs). The halogen bonding can thus begin to be considered as a ®rst choice intermolecular interaction in crystal engineering. q
Weakly Bonded Molecular Networks Built from Tetranitro- and Tetracyanospirobifluorenes
Crystal Growth & Design, 2005
Three tetranitro and three tetracyano derivatives of 9,9′-spirobifluorene were synthesized and crystallized, and their structures were determined by X-ray crystallography. 2,2′,7,7′-Tetranitro-9,9′-spirobi[9Hfluorene] (4) self-associates via C-H‚‚‚O interactions to give an open supramolecular network, with 31% of the total volume of the crystal available for including guests. Tetracyano analogue 5 also crystallizes to give a porous network, but no significant C-H‚‚‚N interactions are present; instead, molecular association is directed primarily by π-stacking. An extended tetranitro analogue, 2,2′,7,7′-tetrakis(4-nitrophenyl)-9,9′-spirobi[9H-fluorene] (6), crystallizes as a nearly close-packed structure held together by a combination of C-H‚‚‚O interactions and π-stacking. Tetracyano analogue 7 crystallizes to form an open structure maintained by π-stacking, without significant C-H‚‚‚N contacts. Extended meta-substituted analogues, 2,2′,7,7′-tetrakis(3-nitrophenyl)-9,9′-spirobi[9H-fluorene] (8) and 2,2′,7,7′-tetrakis(3cyanophenyl)-9,9′-spirobi[9H-fluorene] (9), were also synthesized and crystallized. The two structures are closely similar and show close-packed architectures involving mainly π-stacking. Together, these observations suggest that cyano groups are not effective acceptors for the formation of C-H‚‚‚N interactions strong enough to direct molecular association in competition with aryl-aryl interactions, at least in the spirobifluorene system. In contrast, nitro groups can be used to help direct association via C-H‚‚‚O interactions, either in competition with or in cooperation with other weak interactions.
Tetrahedron, 2000
ÐThe formation of in®nite 1D networks where diiodoper¯uorocarbons are halogen bonded to di-nitrogen substituted hydrocarbons is described. The N´´´I non-covalent interaction is speci®c, directional, and strong enough to effectively overcome the low af®nity between per¯uorocarbon and hydrocarbon modules and to drive their self-assembly in the solid and liquid phase. Several analytical techniques are used to identify and characterise the electron donation from nitrogen to iodine atoms. The effectiveness of the interaction is largely independent from the overall structure of the involved modules. Indeed, supramolecular architectures have been obtained starting from diiodoper¯uoroalkanes and-arenes (electron poor motifs) as well as from pyridine derivatives and di-or trialkylamines (electron rich motifs). The halogen bonding can thus begin to be considered as a ®rst choice intermolecular interaction in crystal engineering.
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