Author: Christian Näther

0000000001304358

AUTHOR

Christian Näther

Effiziente Umwandlung von Licht in chemische Energie: Gerichtete, chirale Photoschalter mit sehr hohen Quantenausbeuten

Coordination-Induced Spin-State Switching with Nickel Chlorin and Nickel Isobacteriochlorin

We present the first coordination-induced spin-state switching with nickel chlorin and nickel isobacteriochlorin. The spin-state switching was monitored by UV-vis spectroscopy and NMR titration experiments. The association constants (K1 and K2) and thermodynamic parameters (ΔH and ΔS) of the coordination of pyridine were determined. The first X-ray analyses of a paramagnetic nickel chlorin and a nickel isobacteriochlorin provide further information about the structure of the octahedral complexes. Nickel chlorin and even more pronounced nickel isobacteriochlorin exhibit stronger coordination of axial ligands compared to the corresponding nickel porphyrin and thus provide the basis for more e…

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Five-Coordinate Complexes [FeX(depe)2]BPh4, X = Cl, Br: Electronic Structure and Spin-Forbidden Reaction with N2

The bonding of N(2) to the five-coordinate complexes [FeX(depe)(2)](+), X = Cl (1a) and Br (1b), has been investigated with the help of X-ray crystallography, spectroscopy, and quantum-chemical calculations. Complexes 1a and 1b are found to have an XP(4) coordination that is intermediate between square-pyramidal and trigonal-bipyramidal. Mössbauer and optical absorption spectroscopy coupled with angular overlap model (AOM) calculations reveal that 1a and 1b have (3)B(1) ground states deriving from a (xz)(1)(z(2))(1) configuration. The zero-field splitting for this state is found to be 30-35 cm(-1). In contrast, the analogous dinitrogen complexes [FeX(N(2))(depe)(2)](+), X = Cl (2a) and Br (…

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Experimental Investigations and ab Initio Studies on Hexacoordinated Complexes of Dichlorosilane

Dichlorosilane, SiH2Cl2, forms two different kinds of coordination compounds with pyridine and 3-picoline: the simple adduct trans-SiH2Cl2(L)2 and the ionic complex [SiH2(L)4]Cl2·4CHCl3 (L = pyridine, 3-picoline). The adducts trans-SiH2Cl2(py)2, 1, and trans-SiH2Cl2(3pic)2, 2, form directly from the reaction of bis(dichlorosilyl)methylamine, NMe(SiHCl2)2 with pyridine (py), and 3-picoline (3pic). Reaction of 1 with an excess of pyridine in chloroform yielded [SiH2(py)4]Cl2·4CHCl3, 3. The molecular and crystal structures of 1−3 were investigated by single-crystal X-ray diffraction. The Si atoms of all three compounds are hexacoordinated and lie on centers of inversion. The basic structural …

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Efficient Conversion of Light to Chemical Energy : Directional, Chiral Photoswitches with Very High Quantum Yields

Abstract Photochromic systems have been used to achieve a number of engineering functions such as light energy conversion, molecular motors, pumps, actuators, and sensors. Key to practical applications is a high efficiency in the conversion of light to chemical energy, a rigid structure for the transmission of force to the environment, and directed motion during isomerization. We present a novel type of photochromic system (diindane diazocines) that converts visible light with an efficiency of 18 % to chemical energy. Quantum yields are exceptionally high with >70 % for the cis–trans isomerization and 90 % for the back‐reaction and thus higher than the biochemical system rhodopsin (64 %). T…

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Self-assembly of 2,8,14,20-tetraisobutyl-5,11,17,23-tetrahydroxyresorc[4]arene

We report herein the observation of a hexameric structure of a hydroxyresorc[4]arene in the solid state, enclosing a large interior space. This artificial molecular container is stabilized only by hydrogen bonds. The tendency to form aggregates in solution is demonstrated mainly by means of ESI-MS methods.

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Evidences for the Formation of Chromium in the Unusual Oxidation State Cr(IV)

Abstract Magnetic measurements on Tl x Cr 5 Se 8 (0≤ x ≤1) reveal that stoichiometric TlCr 5 Se 8 is a three-dimensional antiferromagnet with a Neel temperature T N of about 55 K. In contrast, samples with a reduced Tl content show highly unusual magnetic properties that are without precedent in the literature of magnetically coupled systems: upon lowering the temperature from 300 K the susceptibility reaches a maximum at about 125 K and then steeply drops to a value comparable to that obtained at room temperature. The height of this maximum increases first with decreasing Tl abundance reaching its largest value at a composition Tl 0.2 Cr 5 Se 8 and then decreases again for samples with x 3…

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