Spontaneous Symmetry Breaking of Achiral Molecules Leading to the Formation of Homochiral Superstructures that Exhibit Mechanoluminescence.

Chirality, with its intrinsic symmetry-breaking feature, is frequently utilized in the creation of acentric crystalline functional materials that exhibit intriguing optoelectronic properties. On the other hand, the development of chiral crystals from achiral molecules offers a solution that bypasses the need for enantiopure motifs, presenting a promising alternative and thereby expanding the possibilities of the self-assembly toolkit. Nevertheless, the rational design of achiral molecules that prefer spontaneous symmetry breaking during crystallization has so far been obscure. In this study, we present a series of six achiral molecules, demonstrating that when these conformationally flexible molecules adopt a cis-conformation and engage in multiple non-covalent interactions along a helical path, they collectively self-assemble into chiral superstructures consisting of single-handed supramolecular columns. When these homochiral supramolecular columns align in parallel, they form polar crystals that exhibit intense luminescence upon grinding or scraping. We therefore demonstrate our molecular design strategy could significantly increase the likelihood of symmetry breaking in achiral molecular synthons during self-assembly, offering a facile access to novel chiral crystalline materials with unique optoelectronic properties.

Cocrystals assembled from iodoperfluorobenzene and flexible NTPO via halogen and π-hole bonds.

Two binary cocrystals of 1,4-diiodotetrafluorobenzene (1,4-DITFB, C6F4I2) and 1,3,5-trifluoro-2,4,6-triiodobenzene (1,3,5-TITFB, C6F3I3) with the flexible 2-{[(naphthalen-2-yl)methyl]sulfanyl}pyridine 1-oxide (NTPO, C16H13NOS) molecule were successfully prepared and characterized by X-ray diffraction and quantum chemistry calculation methods. X-ray diffraction analysis reveals that the conformation of the flexible NTPO molecule has been changed significantly after introducing the 1,4-DITFB or 1,3,5-TITFB molecule into the NTPO lattice. Also the formation of the binary cocrystals is driven mainly by robust C-I...-O-N+ halogen bonds and π-hole...π-bond interactions, and they possess `sandwich' structural frameworks. Moreover, interaction energy analysis and AIM analysis were used to explore the contribution of different fragments to the structural stability and the corresponding electronic properties, which reveals that the robust halogen bonds with shorter bonding lengths [2.768 (4) and 2.789 (3) Å] are suggested to be covalent to a certain degree.

Halogen Bonding Adsorbent Pyridine N-oxides for Iodine Capture in Water.

Rapid capture of 129 I with high volatility and toxicity in the environment has attracted much attention. Herein we reported a firstly synthesized nonporous material: pyridine N-oxides (NTPO and ATPO) as iodine adsorbent. Both of NTPO and ATPO exhibit remarkable performance on the adsorption of iodine in aqueous solution, vapor state and organic solvents. Upon the capture of iodine, pyridine N-oxides were transformed to binary cocrystals combined with the pyridine N-oxides and iodine which is driven by halogen bond between iodine and oxygen atoms. Moreover, pyridine N-oxides shows high chemical, thermal and moisture stability.

Ternary Cocrystals with Large Soft Cavities: A 1,4-diiodotetrafluorobenzene (DITFB)⋠4-Biphenylpyridine N-oxide (BPNO) Host Assembled by Inclusion of Planar Aromatic Guests.

A large soft-cavity host composed of 1,4-diiodotetrafluorobenzene (DITFB) and 4-biphenylpyridine N-oxide (BPNO) is assembled under the mediation of a planar aromatic guest molecule (pyrene or perylene) through C-I⋅⋅⋅- O-N+ halogen bonds and π-hole⋅⋅⋅π bonds. Single-crystal X-ray diffraction reveals that guest molecules can be completely encapsulated in the four-layer host cavity to assemble ternary host-guest cocrystals; namely, Pyr@DITFB ⋅ BPNO and Per@DITFB ⋅ BPNO. The luminescence of these ternary cocrystals originates from their discrete guest molecules, which exhibit pure-blue and yellow emissions, respectively, that are localized at 425 nm and in the range of 485 to 578 nm, respectively. In addition, the contribution of different fragments to the stabilization of the crystal structure is estimated by computational chemistry. These cocrystals have significant potential for use in optical applications or materials, such as photonics or organic light-emitting diodes, respectively, that require to avoid the aggregation between luminophores.

π-ring-hole bond around difluoroethyne: stabilization of hydrogen bonding cyclohexamer and dicyclohexamer of ammonia molecules.

The present paper displays new supramolecular structural forms of ammonia molecules. The computation reveals that two novel threading structures of C2F2·(NH3)6 and C2F2·(NH3)12 can be assembled between difluoroethyne and ammonia molecules, in which cyclohexamer (NH3)6 and dicyclohexamer (NH3)12 are constructed by robust N-H···N hydrogen bonds and stabilized all by π-ring-hole···N bonds as supporting spokes of annular structures. More interestingly, annular structures of NH3 still maintain stability as C2F2 is removed. Additionally, the electronic properties and nature of the related noncovalent bonds are explored, which illuminate the important role of π-ring-hole bond for the stabilization of annular structures of NH3. This study could provide valuable insights into chemistry of ammonia, new energy and astronomy aspects by single or multiple noncovalent interactions.Graphical abstract Ammonia molecules can exist stably in dodecahedral cage C2F2·(NH3)12 and (NH3)12 via N-H···N hydrogen bonds and π-ring-hole···N bonds.

The Effect of Electron Donation and Intermolecular Interactions on Ultralong Phosphorescence Lifetime of 4-Carnoyl Phenylboronic Acids.

Purely organic phosphors with persistent room-temperature phosphorescence (RTP) demonstrate promising potential applications in optoelectronic area, bioimaging, and chemical sensing. However, it is still a formidable challenge to further design new organic phosphors due to the unclear mechanism to produce ultralong phosphorescence lifetimes. This paper investigates the correlation between the ultralong phosphorescence lifetime and structure of a series of 4-carbonylphenylboronic acid derivatives in the crystal state. Experimental and calculation results reveal that the electron-donating effect of substituents makes the phosphorescence lifetime longer by not only weakening the vibration relaxation of the excited triplet state but also increasing the energy of T1. Moreover, numerous intermolecular interactions for reducing nonradiative relaxation and the degree of the π-π stacking for stabilizing the triplet state are beneficial to the persistent RTP. The work is conducted to clarify the structure-property correlation of phosphorescent materials and design new persistent phosphors. Finally, an attempt is completed using phosphorescent materials to design two-dimensional or three-dimensional codes and anticounterfeiting applications.

Structural and luminescent properties of co-crystals of tetra-iodo-ethyl-ene with two aza-phenanthrenes.

Two new co-crystals, tetra-iodo-ethyl-ene-phenanthridine (1/2), 0.5C2I4·C13H9N (1) and tetra-iodo-ethyl-ene-benzo[f]quinoline (1/2), 0.5C2I4·C13H9N (2), were obtained from tetra-iodo-ethyl-ene and aza-phenanthrenes, and characterized by IR and fluorescence spectroscopy, elemental analysis and X-ray crystallography. In the crystal structures, C-I⋯π and C-I⋯N halogen bonds link the independent mol-ecules into one-dimensional chains and two-dimensional networks with subloops. In addition, the planar aza-phenanthrenes lend themselves to π-π stacking and C-H⋯π inter-actions, leading to a diversity of supra-molecular three-dimensional structural motifs being formed by these inter-actions. Luminescence studies show that co-crystals 1 and 2 exhibit distinctly different luminescence properties in the solid state at room temperature.

1,3,5-Trifluoro-2,4,6-triiodobenzene: A neglected NIR phosphor with prolonged lifetime by σ-hole and π-hole capture.

Room temperature phosphorescence (RTP) materials have become a hot topic in fields of organic light-emitting dioes, biological sensing and imaging. The present work reports firstly that 1,3,5-trifluoro-2,4,6-triiodobenzene (TITFB) can act as a simple pure organic NIR phosphor due to its novel function in promoting n-π∗ transition. Also, TITFB crystal has longer phosphorescence lifetime than other ordinary multiiodoluminophors and TITFB powder. Based on the TITFB crystal structure, σ-hole and π-hole capture mechanism of n-electron is proposed, i.e., the excited state energy is decreased and n-electrons are stabilized to cause slower radiative decay rate due to the restriction of σ-hole and π-hole bond. Both computational and experimental studies support the mechanism. The new electron-capture mode is more conducive to understanding pure organic ultralong lifetime RTP.

Colorimetric and fluorometric dual sensing of trace water in methanol based on a Schiff Base-Al3+ ensemble probe.

A new julolidine based Schiff base receptor (L) was synthesized and characterized. L forms a 1:1 complex with Al3+ in methanol, resulting in an immediate color change from chartreuse to orange and a remarkable enhancement in its emission intensity along with a bathochromic shift from 540 nm to 570 nm. Addition of trace amounts of water significantly quenches the fluorescence emission, where a decomplexation of Al3+ from the L-Al3+ complex takes place. The significant quenching effect indicated that the L-Al3+ ensemble system can be used to detect trace water in commercial methanol. From the fluorescence titration, the detection limit for sensing water in methanol was estimated to be 0.0047%. We have also made an easy-to-prepare test strip of L-Al3+ to detect water in methanol through naked-eye observation, which is possible to realize in situ monitoring.

Cocrystal assembled by 1,4-diiodotetrafluorobenzene and phenothiazine based on C-I...π/N/S halogen bond and other assisting interactions.

The halogen-bonded cocrystal of 1,4-diiodotetrafluorobenzene (1,4-DITFB) with the butterfly-shape non-planar heterocyclic compound phenothiazine (PHT) was successfully assembled by the conventional solution-based method. X-ray single-crystal diffraction analysis reveals a 3:2 stoichiometric ratio for the cocrystal (1,4-DITFB/PHT), and the cocrystal structure is constructed via C-I...π, C-I...N and C-I...S halogen bonds as well as other assisting interactions (e.g. C-H...F/S hydrogen bond, C-H...H-C and C-F...F-C bonds). The small shift of the 1,4-DITFB vibrational band to lower frequencies in FT-IR and Raman spectroscopies provide evidence to confirm the existence of the halogen bond. In addition, the non-planarity of the PHT molecule in the cocrystal results in PHT emitting weak phosphorescence and relatively strong delayed fluorescence. Thus, a wide range of delayed fluorescence and weak phosphorescence could play a significant role in selecting a proper π-conjugated system to engineer functional cocrystal and luminescent materials by halogen bonds.

Color-tunable phosphorescence of 1,10-phenanthrolines by 4,7-methyl/-diphenyl/-dichloro substituents in cocrystals assembled via bifurcated C-I...N halogen bonds using 1,4-diiodotetrafluorobenzene as a bonding donor.

Single-crystal X-ray diffraction reveals a series of phosphorescent cocrystals which were assembled by 1,4-diiodotetrafluorobenzene (1,4-DITFB) and either 4,7-dimethyl-1,10-phenanthroline (DMPhe), 4,7-diphenyl-1,10-phenanthroline (DPPhe) or 4,7-dichloro-1,10-phenanthroline (DClPhe) via C-I...N halogen bonding. These cocrystals, labeled (1), (2) and (3), respectively, are phosphorescent and a distinct change in phosphorescent color can be observed from orange-yellow, green to yellow-green, with well defined vibrational band maxima at 587, 520 and 611 nm for (1), (2) and (3). Based on the dependence of halogen bonding in sites and strength, we discussed the impact of substituents with different electron-withdrawing effects and steric hindrance on intermolecular noncovalent interactions and phosphorescence. The method of inducing and modulating phosphorescence by halogen bonding and other weak non-covalent interactions through changing the substituent groups of molecules should be significant in both theory and the application of optical function materials with predictable and modulated luminescent properties.

Phosphorescence of several cocrystals assembled by diiodotetrafluorobenzene and three ring angular diazaphenanthrenes via CI···N halogen bond.

X-ray single crystal diffraction reveals that a series of cocrystals are assembled by three ring angular diazaphenanthrenes including 1,7-phenanthroline, 4,7-phenanthroline and 1,10-phenanthroline with 1,4-/1,2-diiodotetrafluorobenzenes via C-I···N halogen bonding (XB) as main driving force. Raman shift of the symmetric CI stretching vibration coupling with ring elongation and lateral ring expansion to a lower frequency by 2 to 7cm-1 for 1,4-DITFB in cocrystals shows the existence of C-I···N halogen bonding. All cocrystals phosphoresce with a distinct change of colors from yellow, orange, pink to red. Also phosphorescent lifetimes of cocrystals containing 1,4-DITFB are longer than those of others constructed by 1,2-DITFB. These phenanthrolines monomers have almost same phosphorescence wavelength (the max. at 493nm) in ß-cyclodextrin solution in the presence of bromocyclohexane as a pure physically heavy atom perturber. The results demonstrate CI···N XB makes heavy atom effect more direct and efficient, and influences significantly the energy level of the lowest lying excited triplet states and the population of electrons to triplet state of the angular diazaphenanthrenes because of greater contribution of lone pair electrons from nitrogen to conjugation systems. Meanwhile, the XB modulates luminescent behaviors due to difference in positions of nitrogen atoms. Good coplanarity, i.e., torsion angles being closer to 0°, in CI···N halogen bonded binary systems also is an important factor affecting the appearance quality of cocrystals.

σ-Hole Bond vs π-Hole Bond: A Comparison Based on Halogen Bond.

The σ-hole and π-hole are the regions with positive surface electrostatic potential on the molecule entity; the former specifically refers to the positive region of a molecular entity along extension of the Y-Ge/P/Se/X covalent σ-bond (Y = electron-rich group; Ge/P/Se/X = Groups IV-VII), while the latter refers to the positive region in the direction perpendicular to the σ-framework of the molecular entity. The directional noncovalent interactions between the σ-hole or π-hole and the negative or electron-rich sites are named σ-hole bond or π-hole bond, respectively. The contributions from electrostatic, charge transfer, and other terms or Coulombic interaction to the σ-hole bond and π-hole bond were reviewed first followed by a brief discussion on the interplay between the σ-hole bond and the π-hole bond as well as application of the two types of noncovalent interactions in the field of anion recognition. It is expected that this review could stimulate further development of the σ-hole bond and π-hole bond in theoretical exploration and practical application in the future.

Strength order and nature of the π-hole bond of cyanuric chloride and 1,3,5-triazine with halide.

The (13)C NMR chemical shift moving upfield indicates the main model of π-holeX(-) bond between cyanuric chloride/1,3,5-triazine (3ClN/3N), which possess both the π-hole and σ-hole, and X(-). (13)C NMR and UV absorption titration in acetonitrile confirmed that the bonding abilities of 3ClN/3N with X(-) follow the order I(-) > Br(-) > Cl(-), which is apparently the order of the charge transfer ability of halide to 3ClN/3N. Chemical calculations showed that the bonding abilities in solution were essentially consistent with those obtained by titration experiments. However, the results in the gas phase were the reverse, i.e., π-holeCl(-) > π-holeBr(-) > π-holeI(-) in bonding energy, which obeys the order of electrostatic interaction. In fact, the π-hole bond and σ-hole bond compete with solvation and possible anion-hydrogen bond between a solvent molecule and a halide in solution. An explanation is that the apparent charge transfer order of π-/σ-holeI(-) > π-/σ-holeBr(-) > π-/σ-holeCl(-) occurs for weak π-hole bonds and σ-hole bonds, whereas the order of electrostatic attraction of π-/σ-holeCl(-) > π-/σ-holeBr(-) > π-/σ-holeI(-) is valid for strong bonds. It can be concluded by combining energy decomposition analysis and natural bond orbital analysis that the π-holeX(-) bond and σ-holeX(-) bond are electrostatically attractive in nature regardless of whether the order is I(-) > Br(-) > Cl(-) or the reverse.

Halogen bonding in the design of organic phosphors.

Halogen bonding as a new strategy for introducing heavy atom perturbers in defined stoichiometry in the design of organic phosphors is reviewed. Considering ten novel cocrystals assembled by polyaromatic hydrocarbons (PAHs) and their heterocyclic analogues and haloperfluorobenzenes using the new strategy, apart from biphenyl cocrystals they all phosphoresce strongly, showing that the new methodology can induce phosphorescence by a heavy atom effect. More interesting, the phosphorescence properties, including excitation/emission wavelengths and decay dynamics, show dependence on the structure of the PAHs and interaction patterns, which is very important and valuable in modulation of the expected colors of luminescent materials.

The halogen bond between amantadine and iodine and its application in the determination of amantadine hydrochloride in pharmaceuticals.

It is proposed that molecular iodine as a donor could form halogen bonding complexes with amantadine (AMD) and amantadine hydrochloride (AMD-HCl) in chloroform and the resultant charge transfer bands (CT band) would be located at 259 and 253 nm, respectively. The halogen bonding interaction was explored by UV absorption, Raman and X-ray crystallography, and a new bonding model named N(+)···N(lep) bond in crystal was observed. The halogen bonding complexes were utilized in the development of simple and accurate spectrophotometry for the analysis of AMD/AMD-HCl. Compared with the traditional method based on the absorption of I3(-) at 290 and 365 nm, the new proposed spectrometry based on the CT band of halogen bonding complex was more sensitive and selective for the detection of AMD/AMD-HCl. Linear relationships with good correlation coefficients (>0.9994) were obtained between the absorbance and the AMD/AMD-HCl concentration in the range of 10-180 µg mL(-1) for AMD-HCl and 0.2-13 µg mL(-1) for AMD. The limit of detection (LOD) was 2.23 µg mL(-1) and limit of quantification (LOQ) was 7.45 µg mL(-1) for AMD-HCl. And because of the stronger bond constant between AMD and iodine than AMD-HCl, the method is more sensitive for AMD; the LOD was 0.02 µg mL(-1) and LOQ was 0.08 µg mL(-1) which was 100 times lower than that of AMD-HCl.

The competition of σ-hole···Cl(-) and π-hole···Cl(-) bonds between C6F5X (X = F, Cl, Br, I) and the chloride anion and its potential application in separation science.

On the basis of the varying amplitude and patterns of the (19)F NMR chemical shift of C6F5X (X = F, Cl, Br, I) in the presence of chloride anions, bonding models of C6F5X·Cl(-) complexes were tentatively established, and the relevant binding constants were obtained. Interaction models were also simulated using computational chemistry. The theoretical computations were found to be highly consistent with the results of the experiments. The results show that C6F5Br/C6F5I and Cl(-) were prone to forming C-I/Br···Cl(-) σ-hole bonding complexes with the (19)F NMR signal shifting to higher fields, and the interaction strength of the C6F5I···Cl(-) σ-hole bond was larger than that of C6F5Br···Cl(-); C6F6/C6F5Cl and Cl(-) formed π-hole···Cl(-) bonding complexes with the signal shifting to lower fields, and the interaction strength of C6F6 was larger than that of C6F5Cl. The binding constant of the C6F5I···Cl(-) σ-hole bonding complex is 38.0 M(-1), which is nearly 165- to 345-fold larger than that of the other C6F5X·Cl(-) complexes. On the basis of the above results, solid phase extraction experiments were designed, and the results demonstrated the potential applicability of the C-I···Cl(-) σ-hole bond in separation science.

Synthesis of a novel fluorescent probe based on 7-nitrobenzo-2-oxa-1,3-diazole skeleton for the rapid determination of vitamin B12 in pharmaceuticals.

A new fluorescent probe, 4-N,N-di(2-hydroxyethyl)imino-7-nitrobenzo-2-oxa-1,3-diazole (HINBD) was synthesized in a single step with reasonably good yield. The water-soluble HINBD emits strongly in the visible region (λex = 479 nm, λem = 545 nm) and is stable over a wide range of pH values. It was found that vitamin B12 (VB12 ) had the ability to quench the fluorescence of HINBD, and the quenched fluorescence intensity was proportional to the concentration of VB12 . A method for VB12 determination based on the quenching fluorescence of HINBD was thus established. Interference effects of various substances, including sugars, vitamins, amino acids, inorganic cations and some organic substances have been studied. Under optimal conditions, the linear range is 0.0-2.4 × 10(-5) mol/L. The determination limit is 8.3 × 10(-8) mol/L. The method was applied to measure VB12 in pharmaceutical preparations with satisfactory results.

The competition of C-X⋯O=P halogen bond and π-hole⋯O=P bond between halopentafluorobenzenes C6F5X (X=F, Cl, Br, I) and triethylphosphine oxide.

Calculation predicted the interacting forms of halopentafluorobenzene C6F5X (X=F, Cl, Br, I) with triethylphosphine oxide which is biologically interested and easily detected by (31)P NMR. The interaction energy and geometric parameters of resultant halogen or π-hole bonding complexes were estimated and compared. Moreover, the bonding constants were determined by (31)P NMR. Both theory and experiments indicated the C6F6 and C6F5Cl interact with triethylphosphine oxide by π-hole bonding pattern, while C6F5I by halogen/σ-hole bonding form. For C6F5Br, two interactions are comparative and should coexist competitively. The calculated interaction energies of σ-hole bonding complexes, -5.07 kcal mol(-1) for C6F5Br⋯O=P and -8.25 kcal mol(-1) for C6F5I⋯O=P, and π-hole bonding complexes, -7.29 kcal mol(-1) for C6F6⋯O=P and -7.24 kcal mol(-1) for C6F5Cl⋯O=P, are consistent with the changing tendency of bonding constants measured by (31)P NMR, 4.37, 19.7, 2.42 and 2.23 M(-1), respectively.

Anionic 3D cage networks self-assembled by iodine and V-shaped pentaiodides using dimeric oxoammonium cations produced in situ as templates.

A novel co-crystal, [(BTEMPO)2(2+)·4I2·2I5(-)] (BTEMPO(+) = 4-benzoyloxy-2,2,6,6-tetramethylpiperidinyl-1-oxoammonium cation), was successfully constructed using iodine and 4-benzoyloxy-2,2,6,6-tetramethylpiperidinyl-1-oxy free radical (BTEMPO) as starting materials and was well characterized by XRD, Raman and calculation. The co-crystal possesses a fascinating 3D anionic cage structure formed by V-shaped-pentaiodides and iodine via multiple halogen bonding and on a template of dimeric (BTEMPO)2(2+) cations. The cationic dimers are held together by a pair of reversed C-H···O=C hydrogen bonds and stabilized the 3D cage structure by C-H···I hydrogen bonds between methyl-protons of BTEMPO(+) and iodine in the framework. The reaction mechanism of producing BTEMPO(+) and I5(-) is proposed and verified by UV-Vis spectroscopy and ESI-MS, which initially goes through a halogen bonding complex between iodine and BTEMPO free radical and then Milliken inner charge transfer and charge separation reaction. UV-Vis absorption spectroscopy confirms the halogen bonding complex between I2 and BTEMPO with a formation constant of 6.94 M(-1) and a 1 : 1 stoichiometry in chloroform. The ESI-MS directly led to observation of the less stable intermediates in the mechanism. It is believed that the mechanism proposed here is helpful in understanding the interactions between I2 and organic electron donors, which are debated frequently, and fills the gaps in the reaction mechanism of I2 with free radicals or analogues.