context of our studies aimed at the preparation of new sulfur containing compounds with unusual structures, i.e., strong intra and intermolecular S S non-bonded interactions (cf. [13]), we tried to synthesize tetrathiaacepentalene derivatives such as 6 starting from diethyl dihydroxythieno[2,3-b]-thiophenedicarboxylate (8) [14]. The bond­ ing situation of 6 would be related to that of the tetrathiapentalene derivative 7 [15].

Angewandte ChemieVolume 94, Issue 3 p. 202-202 Zuschriften Konkurrenz von Aza-Cope-Umlagerung und Aldoladdition† Prof. Dr. Rudolf Gompper, Prof. Dr. Rudolf Gompper Institut für Organische Chemie der Universität Karlstraße 23, D-8000 München 2Search for more papers by this authorDr. Bernhard Kohl, Dr. Bernhard Kohl Institut für Organische Chemie der Universität Karlstraße 23, D-8000 München 2Search for more papers by this author Prof. Dr. Rudolf Gompper, Prof. Dr. Rudolf Gompper Institut für Organische Chemie der Universität Karlstraße 23, D-8000 München 2Search for more papers by this authorDr. Bernhard Kohl, Dr. Bernhard Kohl Institut für Organische Chemie der Universität Karlstraße 23, D-8000 München 2Search for more papers by this author First published: März 1982 https://doi.org/10.1002/ange.19820940305Citations: 8 † Diese Arbeit wurde vom Fonds der Chemischen Industrie unterstützt. AboutPDF ToolsRequest permissionAdd to favorites ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinkedInRedditWechat No abstract is available for this article.Citing Literature Volume94, Issue3März 1982Pages 202-202 This is the German version of Angewandte Chemie. Note for articles published since 1962: Do not cite this version alone. Take me to the International Edition version with citable page numbers, DOI, and citation export. We apologize for the inconvenience. RelatedInformation

Tetrakis[4-(arylpyrimidyl)phenyl]methanes 4 can be readily synthesized by using a highly convergent vinamidinium salt cyclocondensation strategy. The conjugated side-chains of these novel nanostructures display interesting cooperative electronic features such as intramolecular exciplex coupling and ECEC redox processes in the cathodic region.

Potential photosynthetic models, porphyrin dyads with various acceptors, that are separated by a diazaphenylene spacer, are synthesized by a new strategy. The amidine and vinamidinium salts are coupled by pyrimidine rings. In one example (n=1 in the figure), excitation of a flavin acceptor results in energy transfer to the porphyrin singlet (≈60 %) and population of a charge-separated state (≈40 %), which relaxes to the ground state on a subnanosecond time scale.

The reaction of vinamidinium salts with para-substituted aromatic diamines gives rise to polymeric 2-aryl malonaldehyde dianils in good yelds. polymeric cyanines can be obtianed from tetramethoxypropane and a pentamethine cyanine, respecitvely, and para-substituted aromatic diamines. The degree of polymerisation P-n (n = 10 -40) was estimated by neasuring the intrinisic viscoisty eta. The polymers show high electiral powder conducitivites (sigma = 0.03 - 50 S cm(-1)) after doping with iodine or FeCl3.

The dianion of 2,6-bis(diethylamino)-3,4,7,8-tetrahydro-1,3,5,7-tetraazafulvalene-4,8-dithione (1-2H(+)) reacts with the chloro-bridged platinum(II)-complex [(Et3P)PtCl2](2) to give a dark green (N,S)-bischelate (Et3P)(Cl)Pt(1-2H(+))Pt(Cl)(PEt3) (2). Spectroscopic data and a H-1-/H-1-2D-COSY-NMR-spectra are discussed. Chelation leads to a bathochromic shift of about 200 nm.

Oligoaza derivatives of biphenyl, terphenyl, quaterphenyl, quinquephenyl, sexiphenyl, septiphenyl, octiphenyl, noviphenyl, deciphenyl and dodeciphenyl and poly(pyrimidinylenephenylene) can be synthesized from readily accessible vinamidinium salts and amidines or N,N,N'-tris(trimethylsilyl)amidines. The fluorescence of these systems can be tuned over a wide spectral range by varying number and positions of N atoms. Oligo(diazaphenyls) are thermally and photochemically stable, are easier to reduce than oligophenyls, can be dissolved at any rate in strong acids and show strong blue fluorescence in solution as well as in the solid state.

The title compounds are reversible redox systems. The dithienyltetrathiafulvalene-TCNQ complex shows a very high electrical conductivity.

Tetra-p-tolyl and tetrathienyl substitution of manganese(III) porphyrins in charge-transfer compounds with organic acceptors like tetracyanoethylene is used to modify molecular packing of ferrimagnetically correlated chains in the solid. Ferri- and antiferromagnetically ordered compounds and also borderline situations are realized. The strong influence of the solvent used for crystal growth is exemplified.

Symmetric cyanine dyes of the kind Me(2)N(+)=CH-(CH=CH)(n)-NMe(2) normally exhibit no first hyperpolarizabilities beta but have relatively long absorption wavelengths. Therefore they are not suitable NLO chromophores for second-order applications. However, if these chromophores are converted into octupolar molecules either by coupling an extra aldiminium group onto the dye molecule or by grafting three vinamidinium units onto a benzene ring, NLO chromophores with considerable first hyperpolarizabilities are obtained. To prove this, the beta values of both kinds of octupoles have been determined via hyper-Rayleigh scattering in solution at 1064 nm.

2-Dicyanomethylene-1,3-dithiole-4,5-dithiolate (DCDD) has been prepared and used for the synthesis of transition metal complexes (Bu(4)N)(2)[M(DCDD)(2)], M = Ni, Cu, Zn. The redox properties of the nickel complex are similar to that of (Bu(4)N)(2)[Nj(dmit)(2)] (dmit: 1,3-dithiole-2-thione-4,5 dithiolate). Oxidation of (Bu(4)N)(2)[Ni(DCDD)(2)] yields the monoanionic complex Bu(4)N[Ni(DCDD)(2)] the electron spectrum of which is characterized by a strong NIR absorption at 1135 nm. The crystal structure of Bu(4)N[Ni(DCDD)(2)] shows the anion to be almost planar. Face-to-face stacking of the anions with alternating Ni-Ni distances results in a columnar structure of dimeric anions. The spins of the anions within a dimer are antiferromagnetically coupled. The complex Fc*[Ni(DCDD)(2)] (Fc*: decamethylferrocene) has been prepared by a metathesis reaction using Fc*BF4.

The first hyperpolarizability β of four octupole-like molecules and their dipolar subunits has been measured via the hyper-Rayleigh-scattering technique at 1064 nm. The octupolar molecules are tertiary amines with a fully sp2-hybridized nitrogen as central atom. The peripheral groups are either phenyl or diazabiphenyl units which are acceptor-substituted. The octupolar molecules exhibit high β-values 2.5 to 4 times larger than those of their dipolar subunits at comparable absorption wavelengths.

Tetrathiafulvalene and its derivatives can be chemically or electrochemically oxidized to yield stable radical cation salts which display unusual electrical properties. In order to increase the dimensionality of the system by extending the π‐conjugation and thus stabilizing the metallic state, while at the same time keeping the system small, the tetraiodo‐derivative (see Fig.) has been synthesized and characterized. magnified image

Angewandte ChemieVolume 107, Issue 4 p. 531-534 Zuschrift Bis(dicyanmethylen)- und Bis(cyanimino)-Derivate des Indigos und Thioindigos† Prof. Dr. Rudolf Gompper, Corresponding Author Prof. Dr. Rudolf Gompper Institut für Organische Chemie der Universität, Karlstraße 23, D-80333 München, Telefax: Int. + 89/5902-420Institut für Organische Chemie der Universität, Karlstraße 23, D-80333 München, Telefax: Int. + 89/5902-420Search for more papers by this authorDr. Karsten Hartmann, Dr. Karsten Hartmann Institut für Organische Chemie der Universität, Karlstraße 23, D-80333 München, Telefax: Int. + 89/5902-420Search for more papers by this authorDr. Robert Kellner, Dr. Robert Kellner Institut für Organische Chemie der Universität, Karlstraße 23, D-80333 München, Telefax: Int. + 89/5902-420Search for more papers by this authorDr. Kurt Polborn, Dr. Kurt Polborn Institut für Organische Chemie der Universität, Karlstraße 23, D-80333 München, Telefax: Int. + 89/5902-420Search for more papers by this author Prof. Dr. Rudolf Gompper, Corresponding Author Prof. Dr. Rudolf Gompper Institut für Organische Chemie der Universität, Karlstraße 23, D-80333 München, Telefax: Int. + 89/5902-420Institut für Organische Chemie der Universität, Karlstraße 23, D-80333 München, Telefax: Int. + 89/5902-420Search for more papers by this authorDr. Karsten Hartmann, Dr. Karsten Hartmann Institut für Organische Chemie der Universität, Karlstraße 23, D-80333 München, Telefax: Int. + 89/5902-420Search for more papers by this authorDr. Robert Kellner, Dr. Robert Kellner Institut für Organische Chemie der Universität, Karlstraße 23, D-80333 München, Telefax: Int. + 89/5902-420Search for more papers by this authorDr. Kurt Polborn, Dr. Kurt Polborn Institut für Organische Chemie der Universität, Karlstraße 23, D-80333 München, Telefax: Int. + 89/5902-420Search for more papers by this author First published: 21. Februar 1995 https://doi.org/10.1002/ange.19951070429Citations: 2 † Diese Arbeit wurde von der Deutschen Forschungsgemeinschaft und dem Fonds der Chemischen Industrie gefördert. AboutPDF ToolsRequest permissionAdd to favorites ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinked InRedditWechat Citing Literature Volume107, Issue421. Februar 1995Pages 531-534 This is the German version of Angewandte Chemie. Note for articles published since 1962: Do not cite this version alone. Take me to the International Edition version with citable page numbers, DOI, and citation export. We apologize for the inconvenience. RelatedInformation

Indigo in which O is replaced by C(CN)2 (1) or NCN was prepared for the first time. Both compounds and their derivatives absorb in the near-IR at considerably longer wavelengths than indigo. Attempts to synthesize the analogous thioindigo derivatives led to compounds 2-4 (X = S, SO2) by reaction sequences that were sometimes unexpected.