Strongly coupled zinc phthalocyanine-tin porphyrin dyad performing ultra-fast single step charge separation over a 34 A distance

A zinc(II) phthalocyanine-tin(IV) porphyrin dyad with a strong electronic coupling was synthesized and upon light excitation shown to exhibit ultra-fast, long-range electron transfer in a single step.     

Spontaneous Reductive Elimination at Iridium(III) Induced by the Strong π-Acceptor Ligand Trifluorophosphane

The reaction of the cyclometalated five-coordinate 16 VE iridium(III) compound [IrCl(H)(P(tBu)₂C₆H₄-κ²P,C)(P(tBu)₂Ph)] ( 1 ) with the strong π-acceptor ligand trifluorophosphane resulted quickly in the quantitative formation of the new iridium(I) complex trans-[IrCl(PF₃)(P(tBu)₂Ph)₂] ( 2 ). This unexpected spontaneous reductive elimination was already observed in reactions of 1 with the very strong π-acceptor ligands CO and NO⁺. First indications during reactions of 1 with lesser strong π-acceptor ligands like alkyl or arylphosphanes did not show this inversion behavior of the cyclometalation. The title species 2 was characterized by spectroscopic methods and its molecular structure in the crystal was confirmed by X-ray crystallography.     

Accumulative charge separation inspired by photosynthesis

Molecular systems that follow the functional principles of photosynthesis have attracted increasing attention as a method for the direct production of solar fuels. This could give a major carbon-neutral energy contribution to our future society. An outstanding challenge in this research is to couple the light-induced charge separation (which generates a single electron-hole pair) to the multielectron processes of water oxidation and fuel generation. New design considerations are needed to allow for several cycles of photon absorption and charge separation of a single artificial photosystem. Here we demonstrate a molecular system with a regenerative photosensitizer that shows two successive events of light-induced charge separation, leading to high-yield accumulation of redox equivalents on single components without sacrificial agents.     

Site-selective detection of vibrational modes of an iron atom in a trinuclear complex

Nuclear inelastic scattering (NIS) experiments on the trinuclear complex [⁵⁷Fe{L-N₄(CH₂Fc)₂} (CH₃CN)₂](ClO₄)₂ have been performed. The octahedral iron ion in the complex was labelled with ⁵⁷Fe and thereby exclusively the vibrational modes of this iron ion have been detected with NIS. The analysis of nuclear forward scattering (NFS) data yields a ferrous low-spin state for the ⁵⁷Fe labelled iron ion. The simulation of the partial density of states (pDOS) for the octahedral low-spin iron(II) ion of the complex by density functional theory (DFT) calculations is in excellent agreement with the experimental pDOS of the complex determined from the NIS data obtained at 80 K. Thereby it was possible to assign almost each of the experimentally observed NIS bands to the corresponding molecular vibrational modes.     

A new sample environment for cryogenic nuclear resonance scattering experiments on single crystals and microsamples at P01, PETRA III

In order to carry out orientation dependent nuclear resonance scattering (NRS) experiments on small single crystals of e.g. iron proteins and/or chemical complexes but also on surfaces and other micrometer-sized samples a 2-circle goniometer including sample positioning optics has been installed at beamline P01, PETRA III, DESY, Hamburg. This sample environment is now available for all users of this beamline. Sample cooling is performed with a cryogenic gas stream which allows NRS measurements in the temperature range from 80 up to 400 K. In a first test this new sample environment has been used in order to investigate the orientation dependence of the nuclear inelastic scattering (NIS) signature of (i) a dinuclear iron(II) spin crossover (SCO) system and (ii) a hydrogen peroxide treated metmyoglobin single crystal.     

The Hilbert series and a-invariant of circle invariants

Let V be a finite-dimensional representation of the complex circle ${\mathbb{C}}^{\times }$ determined by a weight vector $\mathit{a}\in {\mathbb{Z}}^n$. We study the Hilbert series ${\mathrm{Hilb}}_{\mathit{a}}(t)$ of the graded algebra $\mathbb{C}{[V]}^{{\mathbb{C}}_{\mathit{a}}^{\times }}$ of polynomial ${\mathbb{C}}^{\times }$-invariants in terms of the weight vector a of the ${\mathbb{C}}^{\times }$-action. In particular, we give explicit formulas for ${\mathrm{Hilb}}_{\mathit{a}}(t)$ as well as the first four coefficients of the Laurent expansion of ${\mathrm{Hilb}}_{\mathit{a}}(t)$ at $t=1$. The naive formulas for these coefficients have removable singularities when weights pairwise coincide. Identifying these cancelations, the Laurent coefficients are expressed using partial Schur polynomials that are independently symmetric in two sets of variables. We similarly give an explicit formula for the a-invariant of $\mathbb{C}{[V]}^{{\mathbb{C}}_{\mathit{a}}^{\times }}$ in the case that this algebra is Gorenstein. As an application, we give methods to identify weight vectors with Gorenstein and non-Gorenstein invariant algebras.     

Linear bounds for levels of stable rationality

Let G be one of the groups SL _n (ℂ), Sp_2n (ℂ), SO _m (ℂ), O _m (ℂ), or G ₂. For a generically free G-representation V, we say that N is a level of stable rationality for V/G if V/G × ℙ ^N is rational. In this paper we improve known bounds for the levels of stable rationality for the quotients V/G. In particular, their growth as functions of the rank of the group is linear for G being one of the classical groups.