Interfacial halogen bonding probed using force spectroscopy

Abstract

Halogen bonding between complementary organic monolayers was directly observed in an organic environment using force spectroscopy. This non-covalent interaction is significantly affected by the nature of the organic media. We also demonstrated the effect of lateral packing interactions on the optical properties of the monolayers.

The X40×10 Halogen Bonding Benchmark Revisited: Surprising Importance of (n–1)d Subvalence Correlation

“…In order to describe such interactions, the Hobza group presented a new dataset of 40 halogen-containing dimers. 48 This set includes all relevant halogen atoms (F to I) and covers London dispersion (1-4), electrostatic interactions (5-10), stacking of halogenated aromatic rings (11,12), halogen bonding (13)(14)(15)(16)(17)(18)(19)(20)(21)(22)(23)(24)(25)(26), halogen-π interactions (27)(28)(29)(30), and hydrogen bonded complexes (31)(32)(33)(34)(35)(36)(37)(38)(39)(40). This dataset was then extended by considering dimer dissociation curves analogous to the S66x8 set, but with two additional points at more compressed distances: Thus, for each complex, the X40x10 dataset 48 includes ten data points: aside from the dimer at equilibrium distance r e , four compressed dimers (at 0.80r e , 0.85r e , 0.90r e , and 0.95r e ,) and five stretched dimers (1.05r e , 1.10r e , 1.25r e , 1.50r e , and 2.00r e ).…”

Evidence for Interfacial Halogen Bonding

“…A halogen bond is an attractive non‐covalent interaction between a halogen and a nucleophilic species . Halogen bonding has been characterized in fluid solution and in solid state materials with applications in crystal engineering, anion sensing, self‐assembly, biotechnology, and catalysis . Reported herein is kinetic evidence indicating that halogen bonding also occurs at the solid–liquid interface.…”

“…[1][2][3][4][5][6] Halogen bonding has been characterized in fluid solution and in solid state materials with applications in crystal engineering,anion sensing,s elf-assembly,b iotechnology,a nd catalysis. [7][8][9][10][11][12][13][14][15][16][17][18][19][20][21][22] Reported herein is kinetic evidence indicating that halogen bonding also occurs at the solid-liquid interface.T his finding was enabled by systematic characterization of ah omologous series of donor-p-acceptor dyes,v arying only in the identity of two halogen atoms,a tt itanium dioxide acetonitrile interfaces (Scheme 1). Light-induced interfacial electron transfer experiments revealed enhanced photoreactivity when larger,m ore polarizable halogens were employed.…”

The X40x10 Halogen Bonding Benchmark Revisited: Surprising Importance of (n-1)d Subvalence Correlation

“…For instance, noncovalent interactions associated with halogens are expected to have profound implications for drug discovery: 18,24,27,28 many widely-used drugs are halogenated, and now there is good reason to believe that halogen bonds contribute directly to their efficiency. 27 In the context of supramolecular assembly through hydrogen bonds, we mention two recent imaging studies, by atomic force microscopy 29 and by electron microscopy. 30 Our current knowledge regarding noncovalent interactions in halogenated molecules, and particularly of halogen bonds, is primarily based on computational and crystallographic studies of organic molecules and biomolecules.…”

“…In order to describe such interactions, the Hobza group presented a new dataset of 40 halogen-containing dimers. 48 This set includes all relevant halogen atoms (F to I) and covers London dispersion (1-4), electrostatic interactions (5-10), stacking of halogenated aromatic rings (11,12), halogen bonding (13)(14)(15)(16)(17)(18)(19)(20)(21)(22)(23)(24)(25)(26), halogen-π interactions (27)(28)(29)(30), and hydrogen bonded complexes (31)(32)(33)(34)(35)(36)(37)(38)(39)(40). This dataset was then extended by considering dimer dissociation curves analogous to the S66x8 set, but with two additional points at more compressed distances: Thus, for each complex, the X40x10 dataset 48 includes ten data points: aside from the dimer at equilibrium distance r e , four compressed dimers (at 0.80r e , 0.85r e , 0.90r e , and 0.95r e ,) and five stretched dimers (1.05r e , 1.10r e , 1.25r e , 1.50r e , and 2.00r e ).…”