Pseudo-Octahedral Iron(II) Complexes with Near-Degenerate Charge Transfer and Ligand Field States at the Franck-Condon Geometry.

Increasing the metal-to-ligand charge transfer (MLCT) excited state lifetime of polypyridine iron(II) complexes can be achieved by lowering the ligand's π* orbital energy and by increasing the ligand field splitting. In the homo- and heteroleptic complexes [Fe(cpmp)2 ]2+ (12+ ) and [Fe(cpmp)(ddpd)]2+ (22+ ) with the tridentate ligands 6,2''-carboxypyridyl-2,2'-methylamine-pyridyl-pyridine (cpmp) and N,N'-dimethyl-N,N'-di-pyridin-2-ylpyridine-2,6-diamine (ddpd) two or one dipyridyl ketone moieties provide low energy π* acceptor orbitals. A good metal-ligand orbital overlap to increase the ligand field splitting is achieved by optimizing the octahedricity through CO and NMe units between the coordinating pyridines which enable the formation of six-membered chelate rings. The push-pull ligand cpmp provides intra-ligand and ligand-to-ligand charge transfer (ILCT, LL'CT) excited states in addition to MLCT excited states. Ground and excited state properties of 12+ and 22+ were accessed by X-ray diffraction analyses, resonance Raman spectroscopy, (spectro)electrochemistry, EPR spectroscopy, X-ray emission spectroscopy, static and time-resolved IR and UV/Vis/NIR absorption spectroscopy as well as quantum chemical calculations.

Spin-flip luminescence.

In molecular photochemistry, charge-transfer emission is well understood and widely exploited. In contrast, luminescent metal-centered transitions only came into focus in recent years. This gave rise to strongly phosphorescent CrIII complexes with a d3 electronic configuration featuring luminescent metal-centered excited states which are characterized by the flip of a single spin. These so-called spin-flip emitters possess unique properties and require different design strategies than traditional charge-transfer phosphors. In this review, we give a brief introduction to ligand field theory as a framework to understand this phenomenon and outline prerequisites for efficient spin-flip emission including ligand field strength, symmetry, intersystem crossing and common deactivation pathways using CrIII complexes as instructive examples. The recent progress and associated challenges of tuning the energies of emissive excited states and of emerging applications of the unique photophysical properties of spin-flip emitters are discussed. Finally, we summarize the current state-of-the-art and challenges of spin-flip emitters beyond CrIII with d2, d3, d4 and d8 electronic configuration, where we mainly cover pseudooctahedral molecular complexes of V, Mo, W, Mn, Re and Ni, and highlight possible future research opportunities.

Panchromatic Absorption and Oxidation of an Iron(II) Spin Crossover Complex.

In order to expand and exploit the useful properties of d6-iron(II) and d5-iron(III) complexes in potential magnetic, photophysical, or magnetooptical applications, crucial ligand-controlled parameters are the ligand field strength in a given coordination mode and the availability of suitable metal and ligand frontier orbitals for charge-transfer processes. The push-pull ligand 2,6-diguanidylpyridine (dgpy) features low-energy π* orbitals at the pyridine site and strongly electron-donating guanidinyl donors combined with the ability to form six-membered chelate rings for optimal metal-ligand orbital overlap. The electronic ground states of the pseudo-octahedral d6- and d5-complexes mer-[Fe(dgpy)2]2+, cis-fac-[Fe(dgpy)2]2+, and mer-[Fe(dgpy)2]3+ as well as their charge-transfer (CT) and metal-centered (MC) excited states are probed by variable temperature UV/vis absorption, NMR, EPR, and Mössbauer spectroscopy, magnetic susceptibility measurements at variable temperature as well as quantum chemical calculations.

Excited-State Kinetics of an Air-Stable Cyclometalated Iron(II) Complex.

The complex class [Fe(N^N^C)(N^N^N)]+ with an Earth-abundant metal ion has been repeatedly suggested as a chromophore and potential photosensitizer on the basis of quantum chemical calculations. Synthesis and photophysical properties of the parent complex [Fe(pbpy)(tpy)]+ (Hpbpy=6-phenyl-2,2'-bipyridine and tpy=2,2':6',2''-terpyridine) of this new chromophore class are now reported. Ground-state characterization by X-ray diffraction, electrochemistry, spectroelectrochemistry, UV/Vis, and X-ray spectroscopy in combination with DFT calculations proves the high impact of the cyclometalating ligand on the electronic structure. The photophysical properties are significantly improved compared to the prototypical [Fe(tpy)2 ]2+ complex. In particular, the metal-to-ligand absorption extends into the near-IR and the 3 MLCT lifetime increases by 5.5, whereas the metal-centered excited triplet state is very short-lived.

Intrauterine microdialysis reveals cycle-dependent regulation of endometrial insulin-like growth factor binding protein-1 secretion by human chorionic gonadotropin.

OBJECTIVE: To investigate whether hCG may directly influence endometrial differentiation and function. DESIGN: Controlled clinical study. SETTING: Tertiary university center. PATIENT(S): Fifty-six women with infertility. INTERVENTION(S): An intrauterine microdialysis device (IUMD) was developed that consisted of two balloon catheters connected by microdialysis tubing (molecular weight cutoff: 2,000 kDa). The IUMD was inserted into the uterine cavity and perfused with saline for 3 hours. In 45 women, urinary hCG was then added for 5 hours. Eleven women underwent an identical procedure but without the application of hCG. MAIN OUTCOME MEASURE(S): The response of the endometrium was assessed by measuring IGFBP-1 in the perfusate. RESULT(S): Intrauterine secretion of IGFBP-1 was strictly confined to the late secretory phase (>or=10 days after the beginning of the LH peak). This time point marks the closing of the implantation window. The application of hCG did not affect intrauterine IGFBP-1 levels before day 10 but induced a significant decrease of intrauterine IGFBP-1 levels thereafter. There was no significant change of intrauterine IGFBP-1 levels in the controls. CONCLUSION(S): Intrauterine microdialysis allows a dynamic assessment of endometrial paracrine function in vivo. Human chorionic gonadotropin may be involved in the mechanisms regulating endometrial receptivity.