Lariat effect visualized through the bathochromic shift of counter anion absorption

1987 ◽  
pp. 393 ◽  
Author(s):  
Yoshihisa Inoue ◽  
Chiyose Fujiwara ◽  
Kazuhito Wada ◽  
Akira Tai ◽  
Tadao Hakushi
Keyword(s):  
Bathochromic Shift ◽  
Counter Anion ◽  
Lariat Effect

Absorption Spectra of Substituted 2-Phenylindan-1,3-Dion-2-YL Radicals in Solution

1983 ◽  
Vol 38 (12) ◽  
pp. 1337-1341
Author(s):  
J. Zechner ◽  
N. Getoff ◽  
I. Timtcheva ◽  
F. Fratev ◽  
St. Minchef
Keyword(s):  
Free Energy ◽  
Absorption Spectra ◽  
Flash Photolysis ◽  
Bathochromic Shift ◽  
Substitution Effects ◽  
Linear Free Energy Relationship ◽  
Linear Free Energy

Abstract Flash photolysis of a series of 2-phenylindandione-1,3 derivatives substituted in the 4′ position results in both the formation of stable benzylidenephthalides and of phenylindan-1,3-dion-2-yl radicals. The u. v. absorption maxima of these radicals are dependent on the solvent and show a bathochromic shift upon substitution. These substitution effects were correlated by means of a linear free energy relationship. Attempts were made to draw conclusions concerning the changes in the gap of the states involved and their curvature due to substitution.

scholarly journals Fluorinated azobenzenes as supramolecular halogen-bonding building blocks

2019 ◽  
Vol 15 ◽  
pp. 2013-2019 ◽  
Author(s):  
Esther Nieland ◽  
Oliver Weingart ◽  
Bernd M Schmidt
Keyword(s):  
Solid State ◽  
Dft Calculations ◽  
Visible Light ◽  
Half Life ◽  
Photophysical Properties ◽  
Bathochromic Shift ◽  
Halogen Bonding ◽  
Building Blocks ◽  
Partial Overlap

ortho-Fluoroazobenzenes are a remarkable example of bistable photoswitches, addressable by visible light. Symmetrical, highly fluorinated azobenzenes bearing an iodine substituent in para-position were shown to be suitable supramolecular building blocks both in solution and in the solid state in combination with neutral halogen bonding acceptors, such as lutidines. Therefore, we investigate the photochemistry of a series of azobenzene photoswitches. Upon introduction of iodoethynyl groups, the halogen bonding donor properties are significantly strengthened in solution. However, the bathochromic shift of the π→π* band leads to a partial overlap with the n→π* band, making it slightly more difficult to address. The introduction of iodine substituents is furthermore accompanied with a diminishing thermal half-life. A series of three azobenzenes with different halogen bonding donor properties are discussed in relation to their changing photophysical properties, rationalized by DFT calculations.

Interaction of nitric oxide with Ru(II) complexes of deuteroporphyrindimethylester derivatives

2009 ◽  
Vol 13 (01) ◽  
pp. 35-40 ◽  
Author(s):  
Rudy Martin ◽  
Roberto Cao ◽  
Ana M. Esteva ◽  
Franz-Peter Montforts
Keyword(s):  
Nitric Oxide ◽  
Photoelectron Spectroscopy ◽  
Gold Electrode ◽  
Charge Transfer Band ◽  
Bathochromic Shift ◽  
Considerable Change ◽  
Cathodic Peak ◽  
X Ray ◽  
Polycrystalline Gold ◽  
Self Assembled

A new ruthenium(II) porphyrin disulphide derivative, [ Ru ( Pds )( CO )], was obtained from ruthenium(II)(carbonyl)deuteroporphyrin(IX), [ Ru ( DPdc )( CO )] and cystamine. The interaction of this complex with nitric oxide was studied spectrophotometrically and a bathochromic shift of the charge transfer band and considerable change in the α and β bands of the complex were observed. According to the IR spectrum, the product of this interaction is [ Ru ( DmDP )( NO +)( NO 2-)]. [ Ru ( Pds )( CO )] was then self-assembled on polycrystalline gold and characterized by X-ray photoelectron spectroscopy. [ Ru ( Pds )( CO )] was also self-assembled on gold electrode beads and its interaction with nitric oxide in aqueous solution was studied by cyclic voltammetry. A shift in the ruthenium redox process and a new irreversible cathodic peak at -0.59 V were observed, both indicating coordination of NO .

Gemischte Alkalimetall-Oxidosulfidomolybdate A2[MoOxS4– x] (x = 1, 2, 3; A = K, Rb, Cs, NH4). Synthesen, Kristallstrukturen und Eigenschaften / Mixed Alkali Oxidosulfidomolybdates A2[MoOxS4−x] (x = 1, 2, 3; A = K, Rb, Cs, NH4).Synthesis, Crystal Structure and Properties

2012 ◽  
Vol 67 (2) ◽  
pp. 127-22
Author(s):  
Anna J. Lehner ◽  
Korina Kraut ◽  
Caroline Röhr
Keyword(s):  
Bathochromic Shift ◽  
Structure Type ◽  
Structure Theory ◽  
Monoclinic Space Group ◽  
Orthorhombic Space Group ◽  
Space Group ◽  
Coordination Numbers ◽  
Preparation Conditions ◽  
Vis Spectroscopy ◽  
Type Orthorhombic

Mixed sulfido/oxidomolybdate anions [MoOxS4−x]2− (x = 1, 2, 3) have been prepared by passing H2S gas through a solution of oxidomolybdates. The alkali salts of K+, Rb+, Cs+, and NH+4 precipitate as crystalline salts from these solutions depending on the pH, the polarity of the solvent, the educt concentrations and the temperature. Their structures have been determined by means of X-ray single-crystal diffraction data. All trisulfidomolybdates A2[MoOS3] (A = NH4/K/Rb/Cs) are isotypic with the tetrasulfido salts, exhibiting the β -K2[SO4] type (orthorhombic, space group Pnma, Z = 4; for A = Rb: a = 940.62(4), b = 713.32(4), c = 1164.56(5) pm, R1 = 0.0281). In contrast, the disulfidomolybdates exhibit a rich crystal chemistry, forming three different structure types depending on the preparation conditions and the size of the A cation: All four cations form salts crystallizing with the (NH4)2[WO2S2] structure type (monoclinic, space group C2/c, Z = 4, for A = Rb: a = 1144.32(11), b = 732.60(4), c = 978.99(10) pm, β = 120.324(7)°, R1 = 0.0274). For the three alkali metal cations a second polymorph with a new structure type (monoclinic, space group P21/c, Z = 4) is observed in addition (for A = Rb: a = 674.83(2), b = 852.98(3), c = 1383.10(9) pm, β = 115.19(1)°, R1 = 0.0216). The cesium salt also crystallizes with a third modification of another new structure type (orthorhombic, space group Pbcn, Z = 4, a = 915.30(6), b = 777.27(7), c = 1120.02(7) pm, R1 = 0.0350). Only for K, an anhydrous monosulfidomolybdate could be obtained (K2[MoO4] structure type, monoclinic, space group C2/m, Z = 4, a = 1288.7(3), b = 615.7(2), c = 762.2(1) pm, β = 109.59(1)°, R1 = 0.0736). The intramolecular chemical bonding in the molybdate anions is discussed and compared with the respective vanadates. Hereby aspects like bond lengths, bond strengths and force constants derived from Raman spectroscopy, are taken into account. Especially for the polymorphic disulfido salts, in-depth analyses of the local coordination numbers and the packing of the ions are presented. The gradual bathochromic shift of the crystal color with increasing S content and increasing size of the counter cations A and molar volumes (for the polymorphic forms), respectively, is in accordance with the increase of the experimental (UV/Vis spectroscopy) and calculated (FP-LAPW band structure theory) band gaps.

Quinoline-annulated chlorins and chlorin-analogs

2016 ◽  
Vol 20 (01n04) ◽  
pp. 265-273 ◽  
Author(s):  
Joshua Akhigbe ◽  
Mengxi Yang ◽  
Michael Luciano ◽  
Christian Brückner
Keyword(s):  
Absorption Spectra ◽  
Functional Group ◽  
Bathochromic Shift ◽  
Red Shift ◽  
Simple Strategy

The OsO4-mediated dihydroxylation of quinoline-annulated porphyrin generates a quinoline-annulated dihydroxychlorin in a regioselective fashion. Its dihydroxypyrroline moiety, located at the opposite of the annulated pyrrole, is susceptible to the same functional group interconversions we previously demonstrated for non-annulated dihydroxychlorins: oxidations to the corresponding dione, lactone, and dialkoxymorpholine derivatives. The quinoline-annulated chlorin and derivatives are all characterized by absorption spectra that are much broadened and between 130 and 220 nm red-shifted compared to their non-annulated analogs. Absorbance maxima in the NIR up to well above 800 nm were recorded. We attribute the bathochromic shift to their extended [Formula: see text]-systems and inferred non-planarity, highlighting that quinoline-annulation is a particularly effective and simple strategy to red-shift the absorption spectra of chlorins and chlorin analogs.

Synthesis of Imidazolium Salt-Containing Poly(diphenylacetylene)s and the Effect of Counter Anion on Gas Permeability

2014 ◽  
Vol 71 (7) ◽  
pp. 334-337 ◽  
Author(s):  
Hyuma ITO ◽  
Toshikazu SAKAGUCHI ◽  
Tamotsu HASHIMOTO
Keyword(s):  
Gas Permeability ◽  
Counter Anion ◽  
Imidazolium Salt

Effect of the counter anion of cesium on foliar uptake and translocation

2009 ◽  
Vol 100 (1) ◽  
pp. 54-57 ◽  
Author(s):  
Hidenao Hasegawa ◽  
Hirofumi Tsukada ◽  
Hitoshi Kawabata ◽  
Yuki Chikuchi ◽  
Yuichi Takaku ◽  
...  
Keyword(s):  
Foliar Uptake ◽  
Counter Anion
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