scholarly journals Solution and Solid-State Photophysical Properties of Positional Isomeric Acrylonitrile Derivatives with Core Pyridine and Phenyl Moieties: Experimental and DFT Studies

Molecules ◽  
2021 ◽  
Vol 26 (6) ◽  
pp. 1500
Author(s):  
Armando Castillo ◽  
Paulina Ceballos ◽  
Pilar Santos ◽  
Margarita Cerón ◽  
Perumal Venkatesan ◽  
...  
Keyword(s):  
Solid State ◽  
Molecular Electrostatic Potential ◽  
Dipole Moments ◽  
Photophysical Properties ◽  
Stokes Shift ◽  
X Ray Diffraction ◽  
Monoclinic System ◽  
Potential Surfaces ◽  
Space Groups ◽  
Polarity Parameters

The compounds I (Z)-2-(phenyl)-3-(2,4,5-trimethoxyphenyl)acrylonitrile with one side (2,4,5-MeO-), one symmetrical (2Z,2′Z)-2,2′-(1,4-phenylene)bis(3-(2,4,5-trimethoxyphenyl)acrylonitrile), II (both sides with (2,4,5-MeO-), and three positional isomers with pyridine (Z)-2-(pyridin-2- 3, or 4-yl)-3-(2,4,5-trimethoxyphenyl)acrylonitrile, III–V were synthetized and characterized by UV-Vis, fluorescence, IR, H1-NMR, and EI mass spectrometry as well as single crystal X-ray diffraction (SCXRD). The optical properties were strongly influenced by the solvent (hyperchromic and hypochromic shift), which were compared with the solid state. According to the solvatochromism theory, the excited-state (μe) and ground-state (μg) dipole moments were calculated based on the variation of Stokes shift with the solvent’s relative permittivity, refractive index, and polarity parameters. SCXRD analyses revealed that the compounds I and II crystallized in the monoclinic system with the space group, P21/n and P21/c, respectively, and with Z = 4 and 2. III, IV, and V crystallized in space groups: orthorhombic, Pbca; triclinic, P-1; and monoclinic, P21 with Z = 1, 2, and 2, respectively. The intermolecular interactions for compounds I–V were investigated using the CCDC Mercury software and their energies were quantified using PIXEL. The density of states (DOS), molecular electrostatic potential surfaces (MEPS), and natural bond orbitals (NBO) of the compounds were determined to evaluate the photophysical properties.

scholarly journals Studies on Photophysical Properties of Mono-carbonyl Curcumin Analogues: Experimental and Theoretical approach

2018 ◽  
Vol 34 (4) ◽  
pp. 2170-2179
Author(s):  
Manjula Rayanal ◽  
Prasad Pralhad Pujar ◽  
Sridhar D
Keyword(s):  
Excited State ◽  
Ground State ◽  
Dipole Moments ◽  
Photophysical Properties ◽  
Stokes Shift ◽  
Solvent Polarity ◽  
Frontier Molecular Orbital ◽  
Curcumin Analogues ◽  
Td Dft ◽  
Ground State Dipole Moments

The solvatochromic fluorescence behaviour of mono-carbonyl curcumin analogues has been studied in ten different solvents ranging from non-polar to polar. The solvent effect on the spectral properties of analogues has been discussed. The ground state dipole moments were estimated experimentally by Bilot-Kawski equation which is a function of Stokes shift with the solvent polarity parameters and Guggenheim method and theoretically by TD-DFT studies. The excited state dipole moment was determined using Bilot-Kawski equations. The excited state dipole moments for the two molecules were found to be higher than their corresponding ground state dipole moments. Theoretically Frontier molecular orbital (HOMO/ LUMO) energies were determined by Gaussian 09 W software using TD-DFT.

scholarly journals MicroED Elucidation of Diverse Solid-State Packing in a Family of Electron-Deficient Expanded Helicenes

2020 ◽  
Author(s):  
Adrian Samkian ◽  
Gavin R. Kiel ◽  
Christopher G. Jones ◽  
Harrison Bergman ◽  
Julia Oktawiec ◽  
...  
Keyword(s):  
Solid State ◽  
Electron Diffraction ◽  
Rapid Assessment ◽  
Nanometer Scale ◽  
Proof Of Concept ◽  
X Ray Diffraction ◽  
X Ray ◽  
Space Groups ◽  
Indispensable Tool ◽  
Solid State Structures

Solid-state packing plays a defining role in the properties of a molecular organic material, but it is difficult to elucidate in the absence of single crystals that are suitable for X-ray diffraction. Here, we demonstrate the coupling of divergent synthesis with microcrystal electron diffraction (MicroED) for rapid assessment of solid-state packing motifs, using a class of chiral nanocarbons – expanded helicenes – as a proof of concept. Two highly selective oxidative dearomatizations of a readily-accessible helicene provided a divergent route to four electron-deficient analogues containing quinone or quinoxaline units. Crystallization efforts consistently yielded microcrystals that were unsuitable for single crystal X-ray diffraction, but ideal for MicroED. This technique facilitated the elucidation of solid-state structures of all five compounds with <1.1 Å resolution. The otherwise-inaccessible data revealed a range of notable packing behavior, including four different space groups, homochirality in a crystal for a helicene with an extremely low enantiomerization barrier, and nanometer scale cavities. The results of this study suggest that MicroED will soon become an indispensable tool for high-throughput investigations in pursuit of next-generation organic materials.

scholarly journals Synthesis and crystal structure of two new phosphates with Alluaudite type structure: (M, Mn)3Fe(PO4)3 (M= Ca, Cd)

2018 ◽  
Vol 149 ◽  
pp. 01084 ◽  
Author(s):  
Ghaleb Alhakmi ◽  
Abderrazzak Assani ◽  
Mohamed Saadi ◽  
Lahcen El Ammari
Keyword(s):  
Crystal Structure ◽  
Solid State ◽  
Type Structure ◽  
X Ray Diffraction ◽  
Monoclinic System ◽  
Synthesis And Crystal Structure ◽  
X Ray ◽  
Open Framework ◽  
Bivalent Cations ◽  
The Common

Two new phosphates with alluaudite type structure (M, Mn)3Fe(PO4)3 (M= Ca, Cd), namely Ca1.54Mn1.46Fe(PO4)3 and Cd0.66Mn2.34Fe(PO4)3, has been synthesized by a solid state reaction and characterized by single-crystal X-ray diffraction. The two compounds crystallize in the monoclinic system with C2/c space group. Their open framework results from (Fe1/Mn1)2O10 units of edge-sharing (Fe/Mn)O6 octahedra, which alternate with M(1)O6 octahedra (M(1)=Ca1/Mn2 or Cd1/Mn2) that form infinite chains running along [10-1] direction. These chains are linked together through the common corners of PO4 tetrahedra giving rise to two types of tunnels occupied by bivalent cations Ca2+ or Cd2+ and Mn2+.

scholarly journals Photophysical properties and energy transfer mechanism of a praseodymium compound with a two-dimensional layer

2020 ◽  
Vol 44 (5-6) ◽  
pp. 343-348
Author(s):  
Wen-Tong Chen
Keyword(s):  
Energy Transfer ◽  
Solid State ◽  
Hydrothermal Reaction ◽  
Photophysical Properties ◽  
Transfer Mechanism ◽  
Energy Transfer Mechanism ◽  
Two Dimensional ◽  
Monoclinic System ◽  
Reflectance Measurement ◽  
Praseodymium Complex

A hydrothermal reaction results in the formation of a novel [Pr2(2,5-PA)2(2,5-HPA)2(H2O)4] n·2 nH2O complex (2,5-H2PA = 2,5-pyridinedicarboxylic acid). The complex is structurally characterized by single-crystal X-ray diffraction and crystallizes in the space group P21 of the monoclinic system with two formula units in one cell. This praseodymium complex is characterized by a two-dimensional layered structure. A solid-state photoluminescence experiment reveals that the praseodymium complex shows an emission in the red region. The complex has Commission Internationale de I’Éclairage chromaticity coordinates of 0.5495 and 0.4492. The photoluminescence emission bands could be assigned to the characteristic emission of the 4 f electron intrashell transition of the 3 P0 → 3 H5, 1 D2 → 3 H4, 3 P0 → 3 H6, 3 P0 → 3 F2, and 3 P1 → 3 F3 of the Pr3+ ions. The energy transfer mechanism is explained by the energy level diagrams of the praseodymium ions and the 2,5-H2PA ligand. A solid-state diffuse reflectance measurement shows that the complex possesses a wide optical band gap of 3.48 eV.

scholarly journals Effects of Substituents on the Blue Luminescence of Disilane-Linked Donor‒Acceptor‒Donor Triads

Molecules ◽  
2019 ◽  
Vol 24 (3) ◽  
pp. 521 ◽  
Author(s):  
Tsukasa Usuki ◽  
Kenichiro Omoto ◽  
Masaki Shimada ◽  
Yoshinori Yamanoi ◽  
Hidetaka Kasai ◽  
...  
Keyword(s):  
Solid State ◽  
Density Functional ◽  
Photophysical Properties ◽  
Density Functional Theory Calculations ◽  
Molecular Structures ◽  
Optical Measurements ◽  
X Ray Diffraction ◽  
Absolute Quantum Yield ◽  
Donor Acceptor ◽  
Metal Catalyzed

A series of disilane-linked donor‒acceptor‒donor triads (D‒Si‒Si‒A‒Si‒Si‒D) was synthesized to investigate the effects of substituents on the photophysical properties. The triads were prepared by metal-catalyzed diiodosilylation of aryl iodides using a Pd(P(t-Bu)3)2/(i-Pr)2EtN/toluene system that we previously developed. Optical measurements, X-ray diffraction analysis, and density functional theory calculations revealed relationships between the photophysical properties and molecular structures of these triads in solution and in the solid state. The compounds emitted blue to green fluorescence in CH2Cl2 solution and in the solid state. Notably, compound 2 showed fluorescence with an absolute quantum yield of 0.17 in the solid state but showed no fluorescence in CH2Cl2. Our findings confirmed that the substituent adjacent to the disilane moiety affects the conformations and emission efficiencies of compounds in solution and in the solid state.

scholarly journals Counter Anion Effect on the Photophysical Properties of Emissive Indolizine-Cyanine Dyes in Solution and Solid State

Molecules ◽  
2018 ◽  
Vol 23 (12) ◽  
pp. 3051 ◽  
Author(s):  
Jacqueline Gayton ◽  
Shane Autry ◽  
Ryan Fortenberry ◽  
Nathan Hammer ◽  
Jared Delcamp
Keyword(s):  
Thin Films ◽  
Solid State ◽  
Near Infrared ◽  
Photophysical Properties ◽  
Stokes Shift ◽  
Counter Anion ◽  
Anion Effect ◽  
Research Areas ◽  
Active Research ◽  
Stokes Shifts

Near-infrared emissive materials with tunable Stokes shifts and solid-state emissions are needed for several active research areas and applications. To aid in addressing this need, a series of indolizine-cyanine compounds varying only the anions based on size, dipole, and hydrophilicity were prepared. The effect of the non-covalently bound anions on the absorption and emission properties of identical π-system indolizine-cyanine compounds were measured in solution and as thin films. Interestingly, the anion choice has a significant influence on the Stokes shift and molar absorptivities of the dyes in solution. In the solid-state, the anion choice was found to have an effect on the formation of aggregate states with higher energy absorptions than the parent monomer compound. The dyes were found to be emissive in the NIR region, with emissions peaking at near 900 nm for specific solvent and anion selections.

Two mefenamic acid derivatives: structural study using powder X-ray diffraction, Hirshfeld surface and molecular electrostatic potential calculations

2017 ◽  
Vol 232 (5) ◽  
pp. 385-394 ◽  
Author(s):  
Paramita Chatterjee ◽  
Tanusri Dey ◽  
Sarbani Pal ◽  
Alok K. Mukherjee
Keyword(s):  
Electrostatic Potential ◽  
Mefenamic Acid ◽  
Molecular Electrostatic Potential ◽  
Three Dimensional ◽  
Molecular Geometry ◽  
Hirshfeld Surface ◽  
X Ray Diffraction ◽  
Potential Surfaces ◽  
X Ray ◽  
Surface Areas

AbstractTwo mefenamic acid (1) derivatives, prop-2-ynyl 2-(2,3-dimethylphynylamino)benzoate (2) and N′-(dihydro-2H-pyran-4(3H)-ylidene)-2-((2,3-dimethylphenyl)amino)benzohydrazide (3), have been synthesized and their crystal structures have been determined from laboratory powder X-ray diffraction data. The DFT optimized molecular geometry in 2 and 3 agrees closely to that obtained from the crystallographic study. The nature of intermolecular interactions in 2 and 3 has been analyzed through Hirshfeld surfaces and two-dimensional fingerprint plots, and compared with that in the mefenamic acid polymorphs. Intermolecular N–H···N, C–H···O/N and C–H···π(arene) interactions in 2 and 3 assemble molecules into two and three-dimensional supramolecular frameworks, respectively. Hydrogen-bond based interactions in 2 and 3 have been complimented by calculating molecular electrostatic potential surfaces. Hirshfeld surface analyses of 2, 3, three mefenamic acid polymorphs and a few related mefenamic acid derivatives retrieved from the Cambridge Structural Database (CSD) indicate that about 80% of the Hirshfeld surface areas in these compounds are due to H···H and C···H/H···C contacts.

X-Ray Investigations on Some Salts of Hydrazine and Hydrazine Derivatives

1961 ◽  
Vol 5 ◽  
pp. 133-141 ◽  
Author(s):  
M. Stammler ◽  
D. Orcutt
Keyword(s):  
Unit Cell ◽  
X Ray Diffraction ◽  
Monoclinic System ◽  
X Ray ◽  
Space Groups ◽  
Inorganic Acids ◽  
Cell Dimensions ◽  
System Cell ◽  
Diffraction Patterns ◽  
Perchlorate Salt

AbstractThe salts of hydrazine or methyl derivatives of hydrazine were prepared by neutralization of the base with inorganic acids, for instance, HBF4, HClO4, H SO4, and HCl. Upon recrystallization of the product from a suitable solvent, X-ray diffraction patterns were obtained. Hydrazine tetrafluoborate H2N-NH2·HBF4 was found to crystallize in the monoclinic system. Cell dimensions and possible space groups were determined. The corresponding perchlorate salt crystallizes in two forms, one of which is isomorphous with hydrazine tetrafluoborate. The second form seems to be stabilized by small amounts of water.The tetrafluoborate salt was prepared from the 1,1-dimethyl hydrazine. It was found to crystallize in the tetragonal system with a primitive unit cell. The perchlorate salt of this base is isomorphous with the fluoborate but with a slightly larger unit cell. Both materials undergo plastic-like deformation. The general appearance and mechanical properties are similar to those of a hydrocarbon wax. The 1,1-dimethyl hydrazine sulfate and the 1,1-dimethyl hydrazine hydrochloride have a lower symmetry than the HBF4 salt and do not show the wax-like properties of the latter. Based on the study of these chemically related compounds an explanation is offered for the properties of 1,1-dimethyl hydrazine tetrafluoborate in terms of crystalline structure.

Synthesis, structure, photoluminescent, optical and magnetic properties of a novel thulium p-hydroxybenzenesulfonate complex

2019 ◽  
Vol 234 (3) ◽  
pp. 177-182
Author(s):  
Rong-Hua Hu ◽  
Wen-Tong Chen ◽  
Jian-gen Huang
Keyword(s):  
Magnetic Susceptibility ◽  
Solid State ◽  
Diffuse Reflectance ◽  
Magnetic Measurements ◽  
Variable Temperature ◽  
X Ray Diffraction ◽  
Monoclinic System ◽  
X Ray ◽  
Elemental Analyses ◽  
Anti Stokes

Abstract A novel thulium p-hydroxybenzenesulfonate complex [Tm(C6H5O4S)2(H2O)6](C6H5O4S)·3H2O (1) was solvothermally synthesized and characterized by elemental analyses, photoluminescence, solid-state UV/vis diffuse reflectance, magnetic measurements and single-crystal X-ray diffraction. Complex 1 features an ionic structure with the thulium ion possessing a square antiprismatic geometry. Complex 1 crystallized in the monoclinic system with space group P21. Photoluminescent measurements with solid-state sample demonstrate that the anti-Stokes emission bands in the red/NIR spectral region 710 and 812 nm are observed from the Tm3+ 4f intrashell transitions from the 3F2,3 excited states to the 3H6 and 1G4 excited state to the 3H5 state, respectively. Solid-state UV/vis diffuse reflectance spectra of complex 1 show the existence of a wide optical band gap of 3.56 eV. Variable-temperature magnetic susceptibility and field dependence magnetization measurements are also studied and the magnetic susceptibility obeys the Curie-Weiss law (χm=c/(T−θ)) with the value C being of 8.6 K and a negative Weiss constant θ being of −0.2 K.

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