Ruthenium(II)-bis(4'-(4-ethynylphenyl)-2,2':6', 2''-terpyridine) - A versatile synthon in supramolecular chemistry. Synthesis and characterization

A homoleptic ethynyl-substituted ruthenium(II)-bisterpyridine complex representing a versatile synthon in supramolecular chemistry was synthesized and analyzed by NMR spectroscopy, mass spectrometry and X-ray diffractometry. Furthermore, its photophysical properties were detailed by UV/Vis absorption, emission and resonance Raman spectroscopy. In order to place the results obtained in the context of the vast family of ruthenium coordination compounds, two structurally related complexes were investigated accordingly. These reference compounds bear either no or an increased chromophore in the 4̀-position. The spectroscopic investigations reveal a systematic bathochromic shift of the absorption and emission maximum upon increasing chromophore size. This bathochromic shift of the steady state spectra occurs hand in hand with increasing resonance Raman intensities upon excitation of the metal-to-ligand charge-transfer transition. The latter feature is accompanied by an increased excitation delocalization over the chromophore in the 4̀-position of the terpyridine. Thus, the results presented allow for a detailed investigation of the electronic effects of the ethynyl substituent on the metal-to-ligand charge-transfer states in the synthon for click reactions leading to coordination polymers

Neuroendocrine Tumors of the Bronchopulmonary System (Typical and Atypical Carcinoid Tumors): Current Strategies in Diagnosis and Treatment. Conclusions of an Expert Meeting February 2011 in Weimar, Germany

Neuroendocrine tumors (NETs; syn. carcinoid tumors) are highly or moderately differentiated neoplasms. They comprise a large variety of rare and heterogeneous tumors with an estimated incidence of 3-5/100,000/year. They can arise in virtually every internal organ, but mainly occur in the gastroenteropancreatic and bronchopulmonary systems. Around 25% of the NETs are localized in the bronchopulmonary system. Approximately 2% of all lung tumors are NETs. According to the World Health Organization (WHO) classification of lung tumors, bronchopulmonary NETs are subdivided into typical carcinoids (TCs) and atypical carcinoids (ACs). The parameter with the highest impact on NET behavior and prognosis is the histological classification and staging according to the tumor/node/metastasis (TNM) system. The diagnosis of NETs is established by histological examination and the immunohistochemical detection of general neuroendocrine markers, such as chromogranin A (CgA) and synaptophysin. Serum markers and the use of functional imaging techniques are important additive tools to establish the diagnosis of a NET. The only curative option for lung NETs is complete surgical resection. Beyond that, the currently available interdisciplinary therapeutic options are local ablation, biotherapy (somatostatin analogues), or chemotherapy. New therapeutic options such as peptide receptor radionuclide therapy (PRRT) and molecularly targeted therapies achieve promising results and are under further evaluation. This report is a consensus summary of the interdisciplinary symposium ‘Neuroendocrine Tumors of the Lung and of the Gastroenteropancreatic System (GEP NET) - Expert Dialogue' held on February 25-26, 2011 in Weimar, Germany. At this conference, a panel of 23 German experts shared their knowledge and exchanged their thoughts about research, diagnosis, and clinical management of NETs, whereby special attention was paid to NETs of the respiratory trac

Perspectives on weak interactions in complex materials at different length scales

Nanocomposite materials consist of nanometer-sized quantum objects such as atoms, molecules, voids or nanoparticles embedded in a host material. These quantum objects can be exploited as a super-structure, which can be designed to create material properties targeted for specific applications. For electromagnetism, such targeted properties include field enhancements around the bandgap of a semiconductor used for solar cells, directional decay in topological insulators, high kinetic inductance in superconducting circuits, and many more. Despite very different application areas, all of these properties are united by the common aim of exploiting collective interaction effects between quantum objects. The literature on the topic spreads over very many different disciplines and scientific communities. In this review, we present a cross-disciplinary overview of different approaches for the creation, analysis and theoretical description of nanocomposites with applications related to electromagnetic properties

Perspectives on weak interactions in complex materials at different length scales

Nanocomposite materials consist of nanometer-sized quantum objects such as atoms, molecules, voids or nanoparticles embedded in a host material. These quantum objects can be exploited as a super-structure, which can be designed to create material properties targeted for specific applications. For electromagnetism, such targeted properties include field enhancements around the bandgap of a semiconductor used for solar cells, directional decay in topological insulators, high kinetic inductance in superconducting circuits, and many more. Despite very different application areas, all of these properties are united by the common aim of exploiting collective interaction effects between quantum objects. The literature on the topic spreads over very many different disciplines and scientific communities. In this review, we present a cross-disciplinary overview of different approaches for the creation, analysis and theoretical description of nanocomposites with applications related to electromagnetic properties

Zinc(II) bisterpyridine complexes: The influence of the cation on the π-conjugation between terpyridine and the lateral phenyl substituent

The synthesis and photophys. properties of an ethynylphenyl-substituted terpyridine ligand L and its corresponding zinc(II) complex [Zn(L)2](PF6)2, serving as model compds. for self-assembling Zn(II)-based metallopolymers suited for photoluminscent and electroluminescent devices, are presented. The UV-vis spectra are characterized, and the photoluminescence quantum yields are detd. The ground-state structures are calcd. by means of DFT, and the structural key features are approved by exptl. as well as by DFT-calcd. Raman spectra. Special attention is paid to the pi-electron delocalization between phenylene (ph) and pyridine (py) and, in particular, to changes in the ph-py bond due to complexation. The DFT-calcd. ph-py bond shortening in [Zn(L)2](PF6)2 compared to L correlates well with the higher wavenumber of the v(ph-py(trig)) vibration, which involves strong ph-py bond stretching. The higher ellipticity in the ph-py bond due to complexation, calcd. according to Bader's QTAIM indicating the pi-character of a bond, is confirmed by the higher Raman intensity of the v(ph-py(trig)) vibration. The electron d. distributions in the ph-py bond between [Zn(L)2](PF6)2 and L are compared in an inter-Delta r plot, which highlights the changes in the bonding situation of the ph-py bond induced by complex forming. [on SciFinder (R)

Synthesis, characterization, and electro-optical properties of Zn II complexes with pi-conjugated terpyridine ligands

A series of nine zinc(II) complexes containing substituted 4'- phenyl-2,2':6',2"-terpyridines as ligands is synthesized and fully characterized. The ground-state structures of four examples are calculated by means of DFT and their structural features are confirmed by experimental Raman spectroscopy. Special focus is placed on the degree of p-electron delocalization between the terpyridine unit and the attached phenyl moiety. Applying Bader's quantum theory of atoms in molecules (QTAIM) and visualizing the electron-density distribution by intermolecular ¿¿ plots reveals an increase in ellipticity-and therefore p-electron delocalization for phenylvinyl-substituted derivatives compared to phenylethynyl-substituted ones. Experimentally, this is verified by spectroscopic means, because an increase in ellipticity goes along with a pronounced decrease of the HOMO-LUMO energy band gap. Overall, the lateral p-conjugated substituents are found to strongly influence the electro-optical properties of the complexes. In solution, the color of emission can be modulated from violet to cyan (425-487 nm) and high quantum yields (FPL up to 0.60) are observed. Thin solid films of the complexes in a matrix of poly(- methyl methacrylate) have been inkjet-printed, and their photophysical behavior (bright emission, FPL up to 0.30) reveals their potential as new emissive materials for applications in light-emitting devices. © 2009 Wiley-VCH Verlag GmbH & Co. KGaA