scholarly journals Mechanochemical Syntheses of Isostructural Luminescent Cocrystals of 9-Anthracenecarboxylic Acid with two Dipyridines Coformers

Crystals ◽  
2020 ◽  
Vol 10 (10) ◽  
pp. 889
Author(s):  
Torvid Feiler ◽  
Biswajit Bhattacharya ◽  
Adam A. L. Michalchuk ◽  
Vincent Schröder ◽  
Emil List-Kratochvil ◽  
...  
Keyword(s):  
Solid State ◽  
Crystal Engineering ◽  
Density Functional ◽  
Photophysical Properties ◽  
Three Dimensional ◽  
Luminescent Materials ◽  
Primary Role ◽  
X Ray Diffraction ◽  
X Ray ◽  
Interpenetrated Structure

Tuning and controlling the solid-state photophysical properties of organic luminophore are very important to develop next-generation organic luminescent materials. With the aim of discovering new functional luminescent materials, new cocrystals of 9-anthracene carboxylic acid (ACA) were prepared with two different dipyridine coformers: 1,2-bis(4-pyridyl)ethylene and 1,2-bis(4-pyridyl)ethane. The cocrystals were successfully obtained by both mechanochemical approaches and conventional solvent crystallization. The newly obtained crystalline solids were characterized thoroughly using a combination of single crystal X-ray diffraction, powder X-ray diffraction, Fourier-transform infrared spectroscopy, differential thermal analysis, and thermogravimetric analysis. Structural analysis revealed that the cocrystals are isostructural, exhibiting two-fold interpenetrated hydrogen bonded networks. While the O–H···N hydrogen bonds adopts a primary role in the stabilization of the cocrystal phases, the C–H···O hydrogen bonding interactions appear to play a significant role in guiding the three-dimensional assembly. Both π···π and C–H···π interactions assist in stabilizing the interpenetrated structure. The photoluminescence properties of both the starting materials and cocrystals were examined in their solid states. All the cocrystals display tunable photophysical properties as compared to pure ACA. Density functional theory simulations suggest that the modified optical properties result from charge transfers between the ACA and coformer molecules in each case. This study demonstrates the potential of crystal engineering to design solid-state luminescence switching materials through cocrystallization.

Supramolecular arrangement and photophysical properties of a dinuclear cyanophenylboronic acid ester

2018 ◽  
Vol 74 (4) ◽  
pp. 452-459 ◽  
Author(s):  
A. Jaquelin Cárdenas-Valenzuela ◽  
Jesús Baldenebro-López ◽  
Jorge A. Guerrero-Álvarez ◽  
Herbert Höpfl ◽  
Daniel Glossman-Mitnik ◽  
...  
Keyword(s):  
Solid State ◽  
Molecular Orbital ◽  
Crystal Engineering ◽  
Density Functional ◽  
Photophysical Properties ◽  
Three Dimensional ◽  
Building Blocks ◽  
Scanning Calorimetry ◽  
Supramolecular Architectures ◽  
Lowest Unoccupied Molecular Orbital

Boronic esters are useful building blocks for crystal engineering and the generation of supramolecular architectures, including macrocycles, cages and polymers (one-, two- and three-dimensional), with potential utility in diverse fields such as separation, storage and luminescent materials. The novel dinuclear cyanophenylboronic ester described herein, namely 4,4′-(2,4,8,10-tetraoxa-3,9-diboraspiro[5.5]undecane-3,9-diyl)dibenzonitrile, C19H16B2N2O4, was prepared by condensation of 4-cyanophenylboronic acid and pentaerythritol and fully characterized by elemental analysis, IR and NMR (1H and 11B) spectroscopy, single-crystal X-ray diffraction analysis and TG-DSC (thermogravimetry–differential scanning calorimetry) studies. In addition, the photophysical properties were examined in solution and in the solid state by UV–Vis and fluorescence spectroscopies. Density functional theory (DFT) calculations with ethanol as solvent reproduced reasonably well the HOMO (highest occupied molecular orbital) and LUMO (lowest unoccupied molecular orbital) of the title compound. Hirshfeld surface and fingerprint plot analyses are presented to illustrate the supramolecular connectivity in the solid state.

scholarly journals Investigation of Solvatomorphism and Its Photophysical Implications for Archetypal Trinuclear Au3(1-Methylimidazolate)3

Molecules ◽  
2021 ◽  
Vol 26 (15) ◽  
pp. 4404
Author(s):  
Shengyang Guan ◽  
David C. Mayer ◽  
Christian Jandl ◽  
Sebastian J. Weishäupl ◽  
Angela Casini ◽  
...  
Keyword(s):  
Crystal Structure ◽  
Solid State ◽  
Density Functional ◽  
Bulk Material ◽  
Variable Temperature ◽  
Active Phase ◽  
Solvent Free ◽  
X Ray Diffraction ◽  
X Ray ◽  
Aurophilic Interactions

A new solvatomorph of [Au3(1-Methylimidazolate)3] (Au3(MeIm)3)—the simplest congener of imidazolate-based Au(I) cyclic trinuclear complexes (CTCs)—has been identified and structurally characterized. Single-crystal X-ray diffraction revealed a dichloromethane solvate exhibiting remarkably short intermolecular Au⋯Au distances (3.2190(7) Å). This goes along with a dimer formation in the solid state, which is not observed in a previously reported solvent-free crystal structure. Hirshfeld analysis, in combination with density functional theory (DFT) calculations, indicates that the dimerization is generally driven by attractive aurophilic interactions, which are commonly associated with the luminescence properties of CTCs. Since Au3(MeIm)3 has previously been reported to be emissive in the solid-state, we conducted a thorough photophysical study combined with phase analysis by means of powder X-ray diffraction (PXRD), to correctly attribute the photophysically active phase of the bulk material. Interestingly, all investigated powder samples accessed via different preparation methods can be assigned to the pristine solvent-free crystal structure, showing no aurophilic interactions. Finally, the observed strong thermochromism of the solid-state material was investigated by means of variable-temperature PXRD, ruling out a significant phase transition being responsible for the drastic change of the emission properties (hypsochromic shift from 710 nm to 510 nm) when lowering the temperature down to 77 K.

A tale of hydrogen abstraction, initially detectedviaX-ray diffraction

2014 ◽  
Vol 70 (3) ◽  
pp. 250-255 ◽  
Author(s):  
Alice K. Hui ◽  
Chun-Hsing Chen ◽  
Adam M. Terwilliger ◽  
Richard L. Lord ◽  
Kenneth G. Caulton
Keyword(s):  
Solid State ◽  
Density Functional ◽  
Computational Study ◽  
Hydrogen Abstraction ◽  
Open Shell ◽  
X Ray Diffraction ◽  
Neutral Radical ◽  
X Ray ◽  
Chloride Ligand ◽  
Synthetic Reaction

Reaction of a bis-tetrazinyl pyridine pincer ligand, btzp, with a vanadium(III) reagent gives not a simple adduct but dichlorido{3-methyl-6-[6-(6-methyl-1,2,4,5-tetrazin-3-yl-κN2)pyridin-2-yl-κN]-1,4-dihydro-1,2,4,5-tetrazin-1-yl-κN1}oxidovanadium(IV) acetonitrile 2.5-solvate, [V(C11H10N9)Cl2O]·2.5CH3CN, a species which X-ray diffraction reveals to have one H atom added to one of the two tetrazinyl rings. This H atom was first revealed by a short intermolecular N...Cl contact in the unit cell and subsequently established, from difference maps, to be associated with a hydrogen bond. One chloride ligand has also been replaced by an oxide ligand in this synthetic reaction. This formula for the complex, [V(Hbtzp)Cl2O], leaves open the question of both ligand oxidation state and spin state. A computational study of all isomeric locations of the H atom shows the similarity of their energies, which is subject to perturbation by intermolecular hydrogen bonding found in X-ray work on the solid state. These density functional calculations reveal that the isomer with the H atom located as found in the solid state contains a neutral radical Hbtzp ligand and tetravalentd1V center, but that these two unpaired electrons are more stable as an open-shell singlet and hence antiferromagnetically coupled.

Structure, Elastic Constants and XRD Spectra of Extended Solids under High Pressure

MRS Advances ◽  
2018 ◽  
Vol 3 (8-9) ◽  
pp. 499-504 ◽  
Author(s):  
I.G. Batyrev ◽  
S.P. Coleman ◽  
J.A. Ciezak-Jenkins ◽  
E. Stavrou ◽  
J.M. Zaug
Keyword(s):  
Elastic Constants ◽  
Energetic Materials ◽  
Density Functional ◽  
Three Dimensional ◽  
Peak Position ◽  
X Ray Diffraction ◽  
Covalent Bonds ◽  
X Ray ◽  
Extended Solids ◽  
Xrd Patterns

ABSTRACTWe present results of evolutionary simulations based on density functional calculations of a potentially new type of energetic materials called extended solids: P-N and N-H. High-density structures with covalent bonds generated using variable and fixed concentration methods were analysed in terms of thermo-dynamical stability and agreement with experimental X-ray diffraction (XRD) spectra. X-ray diffraction spectra were calculated using a virtual diffraction algorithm that computes kinematic diffraction intensity in three-dimensional reciprocal space before being reduced to a two-theta line profile. Calculated XRD patterns were used to search for the structure of extended solids present at experimental pressures by optimizing data according to experimental XRD peak position, peak intensity and theoretically calculated enthalpy. Elastic constants has been calculated for thermodynamically stable structures of P-N system.

Two new CdII MOFs of 1,4-bis(1H-benzimidazol-1-yl)butane and flexible dicarboxylate ligands: luminescence sensing towards Fe3+

2020 ◽  
Vol 76 (11) ◽  
pp. 1024-1033
Author(s):  
Fang-Hua Zhao ◽  
Shi-Yao Li ◽  
Wen-Yu Guo ◽  
Zi-Hao Zhao ◽  
Xiao-Wen Guo ◽  
...  
Keyword(s):  
Aqueous Solution ◽  
Solid State ◽  
Hydrogen Bonds ◽  
Layer Structure ◽  
Three Dimensional ◽  
Supramolecular Network ◽  
Two Dimensional ◽  
X Ray Diffraction ◽  
X Ray ◽  
Vis Spectroscopy

Two new CdII MOFs, namely, two-dimensional (2D) poly[[[μ2-1,4-bis(1H-benzimidazol-1-yl)butane](μ2-heptanedioato)cadmium(II)] tetrahydrate], {[Cd(C7H10O4)(C18H18N4)]·4H2O} n or {[Cd(Pim)(bbimb)]·4H2O} n (1), and 2D poly[diaqua[μ2-1,4-bis(1H-benzimidazol-1-yl)butane](μ4-decanedioato)(μ2-decanedioato)dicadmium(II)], [Cd2(C10H16O4)2(C18H18N4)(H2O)2] n or [Cd(Seb)(bbimb)0.5(H2O)] n (2), have been synthesized hydrothermally based on the 1,4-bis(1H-benzimidazol-1-yl)butane (bbimb) and pimelate (Pim2−, heptanedioate) or sebacate (Seb2−, decanedioate) ligands. Both MOFs were structurally characterized by single-crystal X-ray diffraction. In 1, the CdII centres are connected by bbimb and Pim2− ligands to generate a 2D sql layer structure with an octameric (H2O)8 water cluster. The 2D layers are further connected by O—H...O hydrogen bonds, resulting in a three-dimensional (3D) supramolecular structure. In 2, the CdII centres are coordinated by Seb2− ligands to form binuclear Cd2 units which are linked by bbimb and Seb2− ligands into a 2D hxl layer. The 2D layers are further connected by O—H...O hydrogen bonds, leading to an 8-connected 3D hex supramolecular network. IR and UV–Vis spectroscopy, thermogravimetric analysis and solid-state photoluminescence analysis were carried out on both MOFs. Luminescence sensing experiments reveal that both MOFs have good selective sensing towards Fe3+ in aqueous solution.

Synthesis, structure and photocatalytic degradation of organic dyes of a copper(II) metal–organic framework (Cu–MOF) with a 4-coordinated three-dimensional CdSO4 topology

2019 ◽  
Vol 75 (8) ◽  
pp. 1053-1059 ◽  
Author(s):  
Lin-Lu Qian ◽  
Zhi-Xiang Wang ◽  
Hai-Xin Tian ◽  
Min Li ◽  
Bao-Long Li ◽  
...  
Keyword(s):  
Photocatalytic Degradation ◽  
Crystal Engineering ◽  
Photoelectron Spectroscopy ◽  
Organic Dyes ◽  
Metal Organic Framework ◽  
Three Dimensional ◽  
X Ray Diffraction ◽  
X Ray ◽  
Metal Organic ◽  
And Storage

Metal–organic frameworks (MOFs) have attracted much interest in the fields of gas separation and storage, catalysis synthesis, nonlinear optics, sensors, luminescence, magnetism, photocatalysis gradation and crystal engineering because of their diverse properties and intriguing topologies. A Cu–MOF, namely poly[[(μ2-succinato-κ2 O:O′){μ2-tris[4-(1,2,4-triazol-1-yl)phenyl]amine-κ2 N:N′}copper(II)] dihydrate], {[Cu(C4H4O4)(C24H18N10)]·2H2O} n or {[Cu(suc)(ttpa)]·2H2O} n , (I), was synthesized by the hydrothermal method using tris[4-(1,2,4-triazol-1-yl)phenyl]amine (ttpa) and succinate (suc2−), and characterized by IR, powder X-ray diffraction (PXRD), luminescence, optical band gap and valence band X-ray photoelectron spectroscopy (VB XPS). Cu–MOF (I) shows a twofold interpenetrating 4-coordinated three-dimensional CdSO4 topology with point symbol {65·8}. It presents good photocatalytic degradation of methylene blue (MB) and rhodamine B (RhB) under visible-light irradiation. A photocatalytic mechanism was proposed and confirmed.

Structure and conformational analysis of a bidentate pro-ligand, C21H34N2S2, from powder synchrotron diffraction data and solid-state DFTB calculations

2009 ◽  
Vol 65 (5) ◽  
pp. 639-646 ◽  
Author(s):  
Edward E. Ávila ◽  
Asiloé J. Mora ◽  
Gerzon E. Delgado ◽  
Ricardo R. Contreras ◽  
Luis Rincón ◽  
...  
Keyword(s):  
Solid State ◽  
Diffraction Data ◽  
Density Functional ◽  
Simulated Annealing Algorithm ◽  
Theoretical Calculations ◽  
Tight Binding ◽  
Van Der Waals Interactions ◽  
Am1 Calculations ◽  
X Ray Diffraction ◽  
X Ray

The molecular and crystalline structure of ethyl 1′,2′,3′,4′,4a′,5′,6′,7′-octahydrodispiro[cyclohexane-1,2′-quinazoline-4′,1′′-cyclohexane]-8′-carbodithioate (I) was solved and refined from powder synchrotron X-ray diffraction data. The initial model for the structural solution in direct space using the simulated annealing algorithm implemented in DASH [David et al. (2006). J. Appl. Cryst. 39, 910–915] was obtained performing a conformational study on the fused six-membered rings of the octahydroquinazoline system and the two spiran cyclohexane rings of (I). The best model was chosen using experimental evidence from 1H and 13C NMR [Contreras et al. (2001). J. Heterocycl. Chem. 38, 1223–1225] in combination with semi-empirical AM1 calculations. In the refined structure the two spiran rings have the chair conformation, while both of the fused rings in the octahydroquinazoline system have half-chair conformations compared with in-vacuum density-functional theory (DFT) B3LYP/6-311G*, DFTB (density-functional tight-binding) theoretical calculations in the solid state and other related structures from X-ray diffraction data. Compound (I) presents weak intramolecular hydrogen bonds of the type N—H...S and C—H...S, which produce delocalization of the electron density in the generated rings described by graph symbols S(6) and S(5). Packing of the molecules is dominated by van der Waals interactions.

A three-dimensional CdIIcoordination framework: poly[di-μ2-aqua-{μ2-1,4-bis[(1H-1,2,4-triazol-1-yl)methyl]benzene-κ2N4:N4′}di-μ3-terephthalato-κ3O:O′:O′′-dicadmium(II)]

2014 ◽  
Vol 70 (11) ◽  
pp. 1025-1028
Author(s):  
Hong Shen
Keyword(s):  
Solid State ◽  
Thermogravimetric Analysis ◽  
Room Temperature ◽  
Three Dimensional ◽  
Fluorescence Emission ◽  
Photoluminescence Properties ◽  
X Ray Diffraction ◽  
Strong Fluorescence ◽  
X Ray ◽  
Methyl Benzene

The title CdIIcoordination polymer, [Cd(C10H8O4)(C12H12N6)0.5(H2O)]n, has been obtained by the hydrothermal method and studied by single-crystal X-ray diffraction, elemental analysis, thermogravimetric analysis, IR spectroscopy and fluorescence spectroscopy. The compound forms a novel three-dimensional framework with 3,8-connected three-dimensional binodal {4.52}2{42.510.612.7.83} topology. An investigation of its photoluminescence properties shows that the compound exhibits a strong fluorescence emission in the solid state at room temperature.

Configurations and conformations of glycosyl sulfoxides

2010 ◽  
Vol 88 (11) ◽  
pp. 1154-1174 ◽  
Author(s):  
Hong Liang ◽  
Micheline MacKay ◽  
T. Bruce Grindley ◽  
Katherine N. Robertson ◽  
T. Stanley Cameron
Keyword(s):  
Solid State ◽  
Dft Calculations ◽  
Gas Phase ◽  
Density Functional ◽  
Lone Pair ◽  
Azido Group ◽  
X Ray Diffraction ◽  
X Ray ◽  
Comparison Of The Results ◽  
P Type

X-ray crystallographic studies of two axial glycosyl sulfoxides having RS configurations (derivatives of phenyl 2-azido-2-deoxy-1-thio-α-d-galactopyranoside S-oxide) show that they adopt anti conformations in the solid state, in contrast to previous observations and assumptions. Density functional theory (DFT) calculations at the B3lYP6–311G+(d,p)/6–31G(d) level confirm that anti conformations of both phenyl and methyl RS glycosyl sulfoxides of 2-azido-2-deoxy-α-d-pyranosides are more stable than exo-anomeric conformations in the gas phase. 1D NOE measurements indicate that the more polar exo-anomeric conformers are only populated to a slight extent in solution. The anti conformations are distorted so that the glycosyl substituents are closer to being eclipsed with H1. This distortion allows S n → σ* overlap if the sulfur lone pair is a p-type lone pair. Evidence for this overlap comes from short C1–S bond distances, as short as the comparable bond distances in the X-ray crystal structure and in the results from DFT calculations for the SS glycoside, which does adopt the expected exo-anomeric conformation, both in the solid state and in solution, and has normal n → σ* overlap. For 2-deoxy derivatives not bearing a 2-azido group, gas-phase DFT calculations at the same level indicate that the anti- and exo-anomeric conformers have comparable stabilities. Comparison of the results of the two series shows that electronegative substituents in equatorial orientations at C2 destabilize conformations with parallel S–O arrangements, the conformation favored by having an endocyclic C–O dipole antiparallel to the S–O dipole, by about 2.5 kcal mol–1 (1 cal = 4.184 J). An equatorial glycosyl sulfoxide, (SS) phenyl 3,4,6-tri-O-acetyl-2-deoxy-2-phthalimido-1-thio-β-d-glucopyranoside S-oxide, also adopts an anti conformation in the solid state as shown by X-ray diffraction. It also adopts this conformation in solution, in contrast to studies of other equatorial glycosyl sulfoxides.

scholarly journals A multinuclear solid state NMR, density functional theory and X-Ray diffraction study of hydrogen bonding in Group I hydrogen dibenzoates

CrystEngComm ◽  
2013 ◽  
Vol 15 (43) ◽  
pp. 8823 ◽  
Author(s):  
Gregory J. Rees ◽  
Stephen P. Day ◽  
Alberth Lari ◽  
Andrew P. Howes ◽  
Dinu Iuga ◽  
...  
Keyword(s):  
Density Functional Theory ◽  
Hydrogen Bonding ◽  
Solid State ◽  
Diffraction Study ◽  
Solid State Nmr ◽  
Density Functional ◽  
X Ray Diffraction ◽  
Functional Theory ◽  
X Ray ◽  
Group I
Sign in / Sign up

Export Citation Format

Share Document