scholarly journals Halogen-Bonded BODIPY Frameworks with Tunable Optical Features

2020 ◽  
Author(s):  
Emrah Özcan ◽  
Burcu Dedeoglu ◽  
Yurii Chumakov ◽  
Ayşe Gül Gürek ◽  
Yunus Zorlu ◽  
...  
Keyword(s):  
Fluorescence Enhancement ◽  
Crystal Packing ◽  
Halogen Bond ◽  
Halogen Bonding ◽  
Band Gaps ◽  
Complex Nature ◽  
Intersystem Crossing ◽  
Optical Band Gaps ◽  
Electrostatic Component ◽  
Crystal Packings

The ability to tune optical features of BODIPY materials is essential for their photo-related application. However, it is challenging to efficiently tune the crystal packing of BODIPY derivatives because of their complex nature. In this study, such control of BODIPY supramolecular assemblies was achieved by designing a BODIPY containing a halogen bond (XB) acceptor (–NO2) and donor (I, Br) to mediate halogen bonding interactions. The mono halogenated 2 and 4 was unable to form XB, whereas 3 and 5 formed isostructural mono-coordinate motif 3, 5-I (1D tubular structure) and symmetric bifurcated motif 5-II (1D zig-zag chains structure) via N-O···I,Br XB interactions. The results show that the dispersion and electrostatic component are the major source of 3, 5-I and 5-II XB formations. The XB interaction between –NO2 and X (I, Br) promote singlet-to-triplet intersystem crossing and triplet-to-singlet reverse intersystem crossing due to delocalization of oxygen electrons partially onto the Br and I. Then this interaction leads to unexpected fluorescence enhancement of 5-II. Finally, the indirect optical band gaps of the 3, 5-I and 5-II were able to be tuned in the range of 1.9–2.50 eV via XB driven crystal packings.

scholarly journals Halogen-Bonded BODIPY Frameworks with Tunable Optical Features

2020 ◽  
Author(s):  
Emrah Özcan ◽  
Burcu Dedeoglu ◽  
Yurii Chumakov ◽  
Ayşe Gül Gürek ◽  
Yunus Zorlu ◽  
...  
Keyword(s):  
Fluorescence Enhancement ◽  
Crystal Packing ◽  
Halogen Bond ◽  
Halogen Bonding ◽  
Band Gaps ◽  
Complex Nature ◽  
Intersystem Crossing ◽  
Optical Band Gaps ◽  
Electrostatic Component ◽  
Crystal Packings

The ability to tune optical features of BODIPY materials is essential for their photo-related application. However, it is challenging to efficiently tune the crystal packing of BODIPY derivatives because of their complex nature. In this study, such control of BODIPY supramolecular assemblies was achieved by designing a BODIPY containing a halogen bond (XB) acceptor (–NO2) and donor (I, Br) to mediate halogen bonding interactions. The mono halogenated 2 and 4 was unable to form XB, whereas 3 and 5 formed isostructural mono-coordinate motif 3, 5-I (1D tubular structure) and symmetric bifurcated motif 5-II (1D zig-zag chains structure) via N-O···I,Br XB interactions. The results show that the dispersion and electrostatic component are the major source of 3, 5-I and 5-II XB formations. The XB interaction between –NO2 and X (I, Br) promote singlet-to-triplet intersystem crossing and triplet-to-singlet reverse intersystem crossing due to delocalization of oxygen electrons partially onto the Br and I. Then this interaction leads to unexpected fluorescence enhancement of 5-II. Finally, the indirect optical band gaps of the 3, 5-I and 5-II were able to be tuned in the range of 1.9–2.50 eV via XB driven crystal packings.

Mechanism and application of halogen bond induced fluorescence enhancement and iodine molecule cleavage in solution

2015 ◽  
Vol 39 (1) ◽  
pp. 262-272 ◽  
Author(s):  
Wen-Sheng Zou ◽  
Sen Lin ◽  
Jia-Yuan Li ◽  
Hong-Qing Wei ◽  
Xiao-Qin Zhang ◽  
...  
Keyword(s):  
Fluorescence Enhancement ◽  
Halogen Bond ◽  
Halogen Bonding ◽  
Iodine Molecule

Halogen bonding between iodine and ciprofloxacin (I⋯N XB) induces I–I cleavage with fluorescence enhancement.

Competition between hydrogen and halogen bonding in the structures of 5,10-dihydroxy-5,10-dihydroboranthrenes

2014 ◽  
Vol 70 (1) ◽  
pp. 157-171 ◽  
Author(s):  
Krzysztof Durka ◽  
Sergiusz Luliński ◽  
Katarzyna N. Jarzembska ◽  
Jaromir Smętek ◽  
Janusz Serwatowski ◽  
...  
Keyword(s):  
Hydrogen Bond ◽  
Density Functional ◽  
Crystal Packing ◽  
Halogen Bond ◽  
Halogen Bonding ◽  
Structural Diversity ◽  
Interesting Case ◽  
Molecular Arrangement ◽  
Supramolecular Arrangements

X-ray crystallographic and computational studies are reported for a series of boranthrenes, substituted with halogen atoms. The role of competitive hydrogen (O—H...O, O—H...F, C—H...O) and halogen (Cl...Cl, O...Br, F...F) bonding interactions on the molecular arrangement in the crystal structures is discussed. The structural analysis and calculations reveal that the O—H...O hydrogen bond in the unsubstituted derivative 5,10-dihydroxy-5,10-dihydroboranthrene, C12H10B2O2, is of moderate strength (ca−20 kJ mol−1), but weaker than that in the related thiophene derivative 4,8-dihydro-4,8-dihydroxy-p-diborino[2,3-b:5,6-b]dithiophene, C8H6B2O2S2(ca−40 kJ mol−1). This is due to shielding of the OH group by the H atoms in the β-position of the boranthrene unit. Structural diversity derived from the flexibility of the O—H...O hydrogen bond facilitates the occurrence of other competitive interactions. For instance, in the 1,6-difluoro derivative, C12H8B2F2O2, the crystal packing results from O—H...F and F...F interactions. In turn, the 1,6-dibromo derivative, C12H8B2Br2O2, is dominated by Br...O halogen-bond interactions. In the most interesting case, the 1,6-dichloro derivative, C12H8B2Cl2O2, molecular disorder leads to the formation of two different supramolecular arrangements co-existing in the crystal lattice, one based on the Cl...Cl and C—H...O bonds, and the other stabilized by O—H...O hydrogen bonds. Calculations performed with density-functional theory (DFT;CRYSTAL09) andPIXELmethodologies show that both lattices are characterized by similar energy values (ca−100 kJ mol−1). A mixed arrangement with random or short-range-ordered molecular orientations can also be expected.

scholarly journals Site Selectivity of Halogen Oxygen Bonding in 5- and 6-Haloderivatives of Uracil

Crystals ◽  
2019 ◽  
Vol 9 (9) ◽  
pp. 467 ◽  
Author(s):  
Portalone
Keyword(s):  
Hydrogen Bonds ◽  
Crystal Packing ◽  
Halogen Bond ◽  
Halogen Bonding ◽  
Carbonyl Oxygen ◽  
X Ray Diffraction ◽  
General Ability ◽  
Site Selectivity ◽  
Electron Donating Groups ◽  
Derivatives Of

Seven 5-and 6-halogenated derivatives of uracil or 1-methyluracil (halogen = Cl, Br, I) were studied by single crystal X-ray diffraction. In contrast with pure 5-halouracils, where the presence of N-H…O and C-H…O hydrogen bonds prevents the formation of other intermolecular interactions, the general ability of pyrimidine nucleobases to provide electron donating groups to halogen bonding was confirmed in three crystals and cocrystals containing uracil with the halogen atom at the C6 position. In the latter compounds, among the two nucleophilic oxygen atoms in the C=O moiety, only the urea carbonyl oxygen O1 can act as halogen bond acceptor, being not saturated by conventional hydrogen bonds. The halogen bonds in pure 6-halouracils are all rather weak, as supported by Hirshfeld surface analysis. The strongest interaction was found in the structure of 6-iodouracil, which displayed the largest (13%) reduction of the sum of van der Waals (vdW) radii for the contact atoms. Despite this, halogen bonding plays a role in determining the crystal packing of 6-halouracils, acting alongside conventional hydrogen bonds.

scholarly journals Atom interaction propensities of oxygenated chemical functions in crystal packings

IUCrJ ◽  
2017 ◽  
Vol 4 (2) ◽  
pp. 158-174 ◽  
Author(s):  
Christian Jelsch ◽  
Yvon Bibila Mayaya Bisseyou
Keyword(s):  
Hydrogen Bonds ◽  
Single Molecule ◽  
Hydrophobic Interactions ◽  
Crystal Packing ◽  
Halogen Bonding ◽  
Hydroxyl Groups ◽  
Oxygenated Hydrocarbons ◽  
Atom Interaction ◽  
Chemical Groups ◽  
Crystal Packings

The crystal contacts of several families of hydrocarbon compounds substituted with one or several types of oxygenated chemical groups were analyzed statistically using the Hirshfeld surface methodology. The propensity of contacts to occur between two chemical types is described with the contact enrichment descriptor. The systematic large enrichment ratios of some interactions like the O—H...O hydrogen bonds suggests that these contacts are a driving force in the crystal packing formation. The same statement holds for the weaker C—H...O hydrogen bonds in ethers, esters and ketones, in the absence of polar H atoms. The over-represented contacts in crystals of oxygenated hydrocarbons are generally of two types: electrostatic attractions (hydrogen bonds) and hydrophobic interactions. While Cl...O interactions are generally avoided, in a minority of chloro-oxygenated hydrocarbons, significant halogen bonding does occur. General tendencies can often be derived for many contact types, but outlier compounds are instructive as they display peculiar or rare features. The methodology also allows the detection of outliers which can be structures with errors. For instance, a significant number of hydroxylated molecules displaying over-represented non-favorable oxygen–oxygen contacts turned out to have wrongly oriented hydroxyl groups. Beyond crystal packings with a single molecule in the asymmetric unit, the behavior of water in monohydrate compounds and of crystals withZ′ = 2 (dimers) are also investigated. It was found in several cases that, in the presence of several oxygenated chemical groups, cross-interactions between different chemical groups (e.g.water/alcohols; alcohols/phenols) are often favored in the crystal packings. While some trends in accordance with common chemical principles are retrieved, some unexpected results can however appear. For example, in crystals of alcohol–phenol compounds, the strong O—H...O hydrogen bonds between two phenol groups turn out to be extremely rare, while cross contacts between phenols and alcohols have enriched occurrences.

scholarly journals Zn(II) Heteroleptic Halide Complexes with 2-Halopyridines: Features of Halogen Bonding in Solid State

Molecules ◽  
2021 ◽  
Vol 26 (11) ◽  
pp. 3393
Author(s):  
Mikhail A. Vershinin ◽  
Marianna I. Rakhmanova ◽  
Alexander S. Novikov ◽  
Maxim N. Sokolov ◽  
Sergey A. Adonin
Keyword(s):  
Solid State ◽  
Quantum Yield ◽  
Crystal Packing ◽  
Halogen Bonding ◽  
Molecular Complexes ◽  
Substituted Pyridines ◽  
Halide Complexes

Reactions between Zn(II) dihalides and 2-halogen-substituted pyridines 2-XPy result in a series of heteroleptic molecular complexes [(2-XPy)2ZnY2] (Y = Cl, X = Cl (1), Br (2), I (3); Y = Br, X = Cl (4), Br (5), I (6), Y = I, X = Cl (7), Br (8), and I (9)). Moreover, 1–7 are isostructural (triclinic), while 8 and 9 are monoclinic. In all cases, halogen bonding plays an important role in formation of crystal packing. Moreover, 1–9 demonstrate luminescence in asolid state; for the best emitting complexes, quantum yield (QY) exceeds 21%.

THE BAND GAP ESTIMATION OF ZINC MANGANESE PHOSPHATE GLASSES

2008 ◽  
Vol 22 (12) ◽  
pp. 1265-1272 ◽  
Author(s):  
S. A. SIDDIQI ◽  
M. A. GHAURI ◽  
M. J. S. BAIG
Keyword(s):  
Electric Fields ◽  
Spectral Dependence ◽  
Transport Mechanism ◽  
Phosphate Glasses ◽  
Band Gaps ◽  
Spectral Energy ◽  
Charge Transport Mechanism ◽  
Optical Band Gaps ◽  
Manganese Phosphate ◽  
Made In

Zinc manganese phosphate glasses ( ZnO - MnO - P 2 O 5) of different compositions are synthesized. The optical band gaps are measured in the UV-VIS region. Photoconduction measurements are also made in the spectral energy range 1.5–6.2 eV. At various applied electric fields, the values of the energy band gaps have been deduced from the spectral dependence curves. Furthermore, the band gaps at zero applied voltage were also obtained for different compositions. The charge transport mechanism in these glasses is studied under the Mott's model.

scholarly journals (Z)-3-[2-(2,4-Dinitrophenyl)hydrazin-1-ylidene]isobenzofuran-1(3H)-one dichloromethane hemisolvate

2014 ◽  
Vol 70 (4) ◽  
pp. o418-o418
Author(s):  
Palak Agarwal ◽  
Pragati Mishra ◽  
Nikita Gupta ◽  
Neelam ◽  
Priyaranjan Sahoo ◽  
...  
Keyword(s):  
Hydrogen Bond ◽  
Benzene Ring ◽  
Dihedral Angle ◽  
Title Compound ◽  
Crystal Packing ◽  
Halogen Bond ◽  
Solvent Molecule ◽  
Twofold Axis ◽  
Bond Interaction ◽  
The Mean

In the title compound, 2C14H8N4O6·CH2Cl2, the dichloromethane solvent molecule resides on a crystallographic twofold axis. The mean plane of the phthalisoimide ring is oriented at a dihedral angle of 32.93 (12)° with respect to the nitro-substituted benzene ring. An intramolecular N—H...O hydrogen bond occurs. The crystal packing features a short Cl...O halogen-bond interaction [3.093 (3) Å].

scholarly journals Adenine as a Halogen Bond Acceptor: A Combined Experimental and DFT Study

Crystals ◽  
2019 ◽  
Vol 9 (4) ◽  
pp. 224 ◽  
Author(s):  
Yannick Roselló ◽  
Mónica Benito ◽  
Elies Molins ◽  
Miquel Barceló-Oliver ◽  
Antonio Frontera
Keyword(s):  
Density Functional ◽  
Halogen Bond ◽  
Lone Pair ◽  
Halogen Bonding ◽  
Density Functional Theory Calculations ◽  
Functional Theory ◽  
Adenine Ring ◽  
Bonding Interaction ◽  
Donor Ability ◽  
Adenine Derivative

In this work, we report the cocrystallization of N9-ethyladenine with 1,2,4,5-tetrafluoro-3,6-diiodobenzene (TFDIB), a classical XB donor. As far as our knowledge extends, this is the first cocrystal reported to date where an adenine derivative acts as a halogen bond acceptor. In the solid state, each adenine ring forms two centrosymmetric H-bonded dimers: one using N1···HA6–N6 and the other N7···HB6–N6. Therefore, only N3 is available as a halogen bond acceptor that, indeed, establishes an N···I halogen bonding interaction with TFDIB. The H-bonded dimers and halogen bonds have been investigated via DFT (Density Functional Theory) calculations and the Bader’s Quantum Theory of Atoms In Molecules (QTAIM) method at the B3LYP/6-311+G* level of theory. The influence of H-bonding interactions on the lone pair donor ability of N3 has also been analyzed using the molecular electrostatic potential (MEP) surface calculations.

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