From diiodo Tröger's bases towards halogen-bonded porous organic crystalline materials

Abstract

Diiodo Tröger's base derivatives proved to be self-complementary tectons that are particularly suitable for the formation of porous supramolecular structures by halogen bonding.

Zwitterionic iodonium species afford halogen bond-based porous organic frameworks

“…30 Among the wealth of porous molecular crystals wherein XB contributes to sustaining the architecture, only two examples that can be considered as 3D XOFs were obtained via (i) cocrystallization of the tetrahedral pyridine-based XB acceptor and 1,3,4,5-tetraiododiuorobenzene to form a di-component XOF 29 and (ii) assembly of a heterotopic tecton to give an unstable 3D XOF. 31 The well-developed strategy of assembly of XB donors with nitrogen-based XB acceptors furnishes, 32,33 in particular, halogen-bonded 3D structures (exhibiting diamondoid-like cage entities), which are promising porous materials; these structures have not been tested as adsorbents. [34][35][36][37][38] In some other cases, assembly of iodine species with N-based XB acceptors provided 2D or 1D architectures, featuring cavities.…”

“…Among the wealth of porous molecular crystals wherein XB contributes to sustaining the architecture, only two examples that can be considered as 3D XOFs were obtained via (i) cocrystallization of the tetrahedral pyridine-based XB acceptor and 1,3,4,5-tetraiododifluorobenzene to form a di-component XOF 29 and (ii) assembly of a heterotopic tecton to give an unstable 3D XOF. 31…”

The combination of halogen and hydrogen bonding: a versatile tool in coordination chemistry

“…The maximum value for the relative electrostatic potential on the iodine atom 0.004 electron/Å is 17.0 kcal/mol for INPBA (Figure S1 in the ESI shows data obtained by molecular density 0.002 electron/Å). This value is intermediate between the relative potential calculated for weak halogenbonding donors such as 2,8-diiodo-6H,12H-5,11methanodibenzodiazocine (11.2 kcal/mol) 35 and the powerful XB donor 1,4-bis(iodoethynyl)benzene (25.2 kcal/mol). 19 The lower ESP value for the iodine atom of N-(4iodophenyl)isonicotinamide (12.2 kcal/mol) (Figure S2 3).…”

“…25,26,27,28 The halogen bonding is expected to generate different supramolecular architectures, including helical chains. 29,30,31,32,33,34,35 1)C( 7)C(4)) and = N(1)C( 7)C(4)C(3)), which allow it to fit the local environment (Chart 1 and Figure 1). The INPBA central CCNC spacer unit is almost planar, as shown by the torsion angle (= 177.3°).…”

Supramolecular Architectures of Polyoxometalate Hybrids Originating from Halogen and Hydrogen‐Bonding Interactions

“…Meanwhile, this interaction also becomes a key driven force during the self‐assemblies of extended structures and can be applied in the design and synthesis of functional supramolecular polymers . In recent years, numerous architectures originating from the self‐assemblies of bifunctional halogen‐bonding molecules have shown special charm on account of their fascinating structure . However, compared to other interactions such as hydrogen bonds, the nature and applications of halogen bond in supramolecular chemistry are still less explored, especially in inorganic or inorganic‐organic systems.…”