Preparation and Properties of Surfactant Complexes of Ruthenium(II)

1979 ◽  
Vol 32 (7) ◽  
pp. 1453 ◽  
Author(s):  
O Johansen ◽  
C Kowala ◽  
AWH Mau ◽  
WHF Sasse
Keyword(s):  
Solid State ◽  
Surface Pressure ◽  
Luminescence Intensity ◽  
Crystal Packing ◽  
Emission Spectra ◽  
Quantum Yields ◽  
Alkyl Chains ◽  
Pressure Area ◽  
Bimolecular Quenching ◽  
Chain Lengths

New surfactant complexes RuM2L2+ have been prepared where M is 2,2'-bipyridyl or o-phenanthro- line and L is one of the 4-alkyl-4'-methyl-2,2'-bipyridyls (8a)-(8e), or one of the 4,4'-dialkyl-2,2'- bipyridyls (9a)-(9e), or 1,1'-(2,2'-bipyridyl-4,4'-diyl)bis(nonadecan-1-one). This diketone was pre- pared from 2,2'-bipyridyl-4,4'-dicarboxylic acid and dioctadecylcadmium; the dialkylbipyridyls were obtained by condensing 4,4'-dimethyl-2,2'-bipyridyl with 5-alkylthiopen-2-carbaldehydes, followed by desulfurization with W5 Raney nickel. Several properties of the new complexes have been compared with those of bis(2,Y-bipyridyl)(dioctadecyl 2,2'-bipyridyl-4,4'-dicarboxy1ate)ruthenium dication (2). Monolayers have been prepared and characterized by surface-pressure area curves; film com- pressibilities and stabilities are related to the lengths of the alkyl chains and to subphase composition. Absorption and emission spectra have been examined. The quantum yields and lifetimes of emission are similar in alcohol and water; with monolayer assemblies they are dependent on subphase com- position, and in the solid state they vary between 0.03-0.18 for Φ and 0.5-1.5 μs for τ, according to the chain lengths, which appear to affect crystal packing. Oxygen quenched the luminescence of solutions and supported monolayers reversibly; Stern- Volmer constants and bimolecular quenching constants are given for: diester complex (2), diketone complex (6), dialkylbipyridyl complexes (5). Except with (2) the original luminescence intensity was restored by drying. Hydrogen was not detected following irradiation with visible light of supported monolayers of pure complexes immersed in water.

Crystal-packing modes determine the solid-state ESIPT fluorescence in highly dipolar 2′-hydroxychalcones

2021 ◽  
Author(s):  
Alix Tordo ◽  
Erwann Jeanneau ◽  
Mathieu Bordy ◽  
Yann Bretonnière ◽  
Jens Hasserodt
Keyword(s):  
Solid State ◽  
Single Crystal ◽  
Crystal Packing ◽  
Xrd Analysis ◽  
Quantum Yields ◽  
Single Crystal Xrd ◽  
Structure Property ◽  
Crystal State ◽  
Structure Property Relationship ◽  
Single Crystal Xrd Analysis

Fifteen easily assembled ESIPT-active 2′-hydroxychalcones were prepared to identify deep-red crystal-state fluorophores with increased quantum yields. Systematic single-crystal XRD analysis furnished trends in the structure–property relationship.

Synthesis and solid-state fluorescence properties of pentacyclic 7-substituted-indeno[1′,2′:4,5]pyrido[2,1-a]isoindol-5-ones

RSC Advances ◽  
2015 ◽  
Vol 5 (4) ◽  
pp. 2715-2723 ◽  
Author(s):  
Z. Chamas ◽  
E. Marchi ◽  
B. Presson ◽  
E. Aubert ◽  
Y. Fort ◽  
...  
Keyword(s):  
Solid State ◽  
Crystal Packing ◽  
Fluorescence Properties ◽  
Quantum Yields ◽  
Solid State Fluorescence ◽  
Packing Analysis

New pentacyclic indeno[1′,2′:4,5]pyrido[2,1-a]isoindol-5-ones were designed which possess quantum yields in the solid state up to 32%. The importance of the substituent in 7-position was highlighted through crystal packing analysis.

Comparison of Luminescent Properties in Solid-State and Polymer Films of Eu(III) Complexes Containing 2-Acylindandione Ligands

2018 ◽  
Vol 762 ◽  
pp. 239-243
Author(s):  
Ilze Malina ◽  
Valdis Kampars
Keyword(s):  
Solid State ◽  
Polymer Films ◽  
Red Light ◽  
Emission Spectra ◽  
Luminescent Properties ◽  
Ternary Complexes ◽  
Quantum Yields ◽  
Excitation Spectra ◽  
Ion Emission ◽  
Narrow Bands

The Europium(III) ternary complexes Eu(BID)3(PHEN) and Eu(MBID)3(PHEN) (BID – 2-benzoyl-1,3-indandione, MBID - 2-(4-methylbenzoyl)-1,3-indandione and PHEN – 1,10-Phenantroline) were synthesized, characterized and incorporated into poly methyl methacrylate (PMMA) and poly-N-vinylcarbazole (PVK) matrixes. Emission properties in solid-state and polymer films were investigated through excitation spectra, emission spectra and absolute photoluminescence quantum yields (PLQY). Both complexes in their solid-state and films exhibited red-light luminescence with narrow bands corresponding to Eu(III) ion emission. In solid-state complexes were characterized with PLQY of 6% and 10%, in PVK matrixes quantum yield dropped down to 4%, however, in PMMA films exhibited similar luminescence PLQY than in solid-state.

The Influence of Nitrogen Position on Charge Carrier Mobility in Enantiopure Aza[6]helicene Crystals

2018 ◽  
Author(s):  
Francesco Salerno ◽  
Beth Rice ◽  
Julia Schmidt ◽  
Matthew J. Fuchter ◽  
Jenny Nelson ◽  
...  
Keyword(s):  
Solid State ◽  
Charge Carrier ◽  
Carrier Mobility ◽  
Chemical Structure ◽  
Crystal Packing ◽  
Charge Carrier Mobility ◽  
Individual Factor ◽  
Charge Mobility ◽  
Order Of Magnitude ◽  
Small Change

<p>The properties of an organic semiconductor are dependent on both the chemical structure of the molecule involved, and how it is arranged in the solid-state. It is challenging to extract the influence of each individual factor, as small changes in the molecular structure often dramatically change the crystal packing and hence solid-state structure. Here, we use calculations to explore the influence of the nitrogen position on the charge mobility of a chiral organic molecule when the crystal packing is kept constant. The transfer integrals for a series of enantiopure aza[6]helicene crystals sharing the same packing were analysed in order to identify the best supramolecular motifs to promote charge carrier mobility. The regioisomers considered differ only in the positioning of the nitrogen atom in the aromatic scaffold. The simulations showed that even this small change in the chemical structure has a strong effect on the charge transport in the crystal, leading to differences in charge mobility of up to one order of magnitude. Some aza[6]helicene isomers that were packed interlocked with each other showed high HOMO-HOMO integrals (up to 70 meV), whilst molecules arranged with translational symmetry generally afforded the highest LUMO-LUMO integrals (40 - 70 meV). As many of the results are not intuitively obvious, a computational approach provides additional insight into the design of new semiconducting organic materials.</p>

scholarly journals Convenient Access to Functionalized Non-Symmetrical Atropisomeric 4,4′-Bipyridines

Compounds ◽  
2021 ◽  
Vol 1 (2) ◽  
pp. 58-74
Author(s):  
Emmanuel Aubert ◽  
Emmanuel Wenger ◽  
Paola Peluso ◽  
Victor Mamane
Keyword(s):  
Solid State ◽  
Intermolecular Interactions ◽  
Medicinal Chemistry ◽  
Crystal Packing ◽  
Cross Coupling ◽  
Coupling Reactions ◽  
Halogen Bonds ◽  
Cross Coupling Reactions ◽  
Cyano Groups ◽  
Post Functionalization

Non-symmetrical chiral 4,4′-bipyridines have recently found interest in organocatalysis and medicinal chemistry. In this regard, the development of efficient methods for their synthesis is highly desirable. Herein, a series of non-symmetrical atropisomeric polyhalogenated 4,4′-bipyridines were prepared and further functionalized by using cross-coupling reactions. The desymmetrization step is based on the N-oxidation of one of the two pyridine rings of the 4,4′-bipyridine skeleton. The main advantage of this methodology is the possible post-functionalization of the pyridine N-oxide, allowing selective introduction of chlorine, bromine or cyano groups in 2- and 2′-postions of the chiral atropisomeric 4,4′-bipyridines. The crystal packing in the solid state of some newly prepared derivatives was analyzed and revealed the importance of halogen bonds in intermolecular interactions.

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%.

scholarly journals Transparent Ion-Exchange Membrane Exhibiting Intense Emission under a Specific pH Condition Based on Polypyridyl Ruthenium(II) Complex with Two Imidazophenanthroline Groups

Membranes ◽  
2021 ◽  
Vol 11 (6) ◽  
pp. 400
Author(s):  
Hajime Kamebuchi ◽  
Satoshi Tamaki ◽  
Atsushi Okazawa ◽  
Norimichi Kojima
Keyword(s):  
Ion Exchange ◽  
Emission Intensity ◽  
Density Functional ◽  
Emission Spectra ◽  
Density Functional Theory Calculations ◽  
Ion Exchange Membrane ◽  
Quantum Yields ◽  
Relative Emission Intensity ◽  
Nafion Film ◽  
Exchange Membrane

The development and the photophysical behavior of a transparent ion-exchange membrane based on a pH-sensitive polypyridyl ruthenium(II) complex, [(bpy)2RuII(H2bpib)RuII(bpy)2](ClO4)4 (bpy = 2,2′-bipyridine, H2bpib = 1,4-bis([1,10]phenanthroline[5,6-d]-imidazol-2-yl)benzene), are experimentally and theoretically reported. The emission spectra of [(bpy)2RuII(H2bpib)RuII(bpy)2]@Nafion film were observed between pH 2 and pH 11 and showed the highest relative emission intensity at pH 5 (λmaxem = 594.4 nm). The relative emission intensity of the film significantly decreased down to 75% at pH 2 and 11 compared to that of pH 5. The quantum yields (Φ) and lifetimes (τ) showed similar correlations with respect to pH, Φ = 0.13 and τ = 1237 ns at pH 5, and Φ = 0.087 and τ = 1014 ns and Φ = 0.069 and τ = 954 ns at pH 2 and pH 11, respectively. These photophysical data are overall considerably superior to those of the solution, with the radiative- (kr) and non-radiative rate constants (knr) at pH 5 estimated to be kr = 1.06 × 105 s−1 and knr = 7.03 × 105 s−1. Density functional theory calculations suggested the contribution of ligand-to-ligand- and intraligand charge transfer to the imidazolium moiety in Ru-H3bpib species, implying that the positive charge on the H3bpib ligand works as a quencher. The Ru-Hbpib species seems to enhance non-radiative deactivation by reducing the energy of the upper-lying metal-centered excited state. These would be responsible for the pH-dependent “off-on-off” emission behavior.

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