Photoactive metal complexes employing Earth‐abundant metal ions are a key to sustainable photophysical and photochemical applications. We exploit the effects of an inversion center and ligand non‐innocence to tune the luminescence and photochemistry of the excited state of the [CrN6] chromophore [Cr(tpe)2]3+ with close to octahedral symmetry (tpe=1,1,1‐tris(pyrid‐2‐yl)ethane). [Cr(tpe)2]3+ exhibits the longest luminescence lifetime (τ=4500 μs) reported up to date for a molecular polypyridyl chromium(III) complex together with a very high luminescence quantum yield of Φ=8.2 % at room temperature in fluid solution. Furthermore, the tpe ligands in [Cr(tpe)2]3+ are redox non‐innocent, leading to reversible reductive chemistry. The excited state redox potential and lifetime of [Cr(tpe)2]3+ surpass those of the classical photosensitizer [Ru(bpy)3]2+ (bpy=2,2′‐bipyridine) enabling energy transfer (to oxygen) and photoredox processes (with azulene and tri(n‐butyl)amine).

The intensely luminescent chromium(III) complexes [Cr(ddpd) ] and [Cr(H tpda) ] show surprising pressure-induced red shifts of up to -15 cm kbar for their sharp spin-flip emission bands (ddpd=N,N'-dimethyl-N,N'-dipyridine-2-yl-pyridine-2,6-diamine; H tpda=2,6-bis(2-pyridylamino)pyridine). These shifts surpass that of the established standard, ruby Al O :Cr , by a factor of 20. Beyond the common application in the crystalline state, the very high quantum yield of [Cr(ddpd) ] enables optical pressure sensing in aqueous and methanolic solution. These unique features of the molecular rubies [Cr(ddpd) ] and [Cr(H tpda) ] pave the way for highly sensitive optical pressure determination and unprecedented molecule-based pressure sensing with a single type of emitter.

The molecular bis-(tris(carbene)borate) manganese(IV) complex [{PhB(MeIm)3}2Mn](OTf)2 shows 2Eg → 4A2g luminescence at 828 nm in the solid state at 85 K; this wavelength is longer by approximately 100 nm than the wavelengths typically observed for manganese(IV) and chromium(III) doped solids and for molecular chromium(III) complexes. Weak luminescence is also observed from a LMCT excited state with an absorption maximum at 500 nm. This represents the first molecular manganese(IV) compound for which luminescence has been reported.

. (2014) Vibrations of the S1 state of fluorobenzene-h5 and fluorobenzene-d5 via resonanceenhanced multiphoton ionization (REMPI) spectroscopy. Journal of Chemical Physics, 141 (24 A note on versions:The version presented here may differ from the published version or from the version of record. If you wish to cite this item you are advised to consult the publisher's version. Please see the repository url above for details on accessing the published version and note that access may require a subscription. We report resonance-enhanced multiphoton ionization spectra of the isotopologues fluorobenzeneh 5 and fluorobenzene-d 5 . By making use of quantum chemical calculations, the changes in the wavenumber of the vibrational modes upon deuteration are examined. Additionally, the mixing of vibrational modes both between isotopologues and also between the two electronic states is discussed. The isotopic shifts lead to dramatic changes in the appearance of the spectrum as vibrations shift in and out of Fermi resonance. Assignments of the majority of the fluorobenzene-d 5 observed bands are provided, aided by previous results on fluorobenzene-h 5 . C 2014 AIP Publishing LLC.[http://dx

Photoactive metal complexes employing Earthabundant metal ions are ak ey to sustainable photophysical and photochemical applications.W ee xploit the effects of an inversion center and ligand non-innocence to tune the luminescence and photochemistry of the excited state of the [CrN 6 ] chromophore [Cr(tpe) 2 ] 3+ with close to octahedral symmetry (tpe = 1,1,1-tris(pyrid-2-yl)ethane). [Cr(tpe) 2 ] 3+ exhibits the longest luminescence lifetime (t = 4500 ms) reported up to date for am olecular polypyridyl chromium(III) complex together with av ery high luminescence quantum yield of F = 8.2 %a t room temperature in fluid solution. Furthermore,t he tpe ligands in [Cr(tpe) 2 ] 3+ are redox non-innocent, leading to reversible reductive chemistry.The excited state redoxpotential and lifetime of [Cr(tpe) 2 ] 3+ surpass those of the classical photosensitizer [Ru(bpy) 3 ] 2+ (bpy = 2,2'-bipyridine) enabling energy transfer (to oxygen) and photoredox processes (with azulene and tri(n-butyl)amine).Supportinginformation and the ORCID identification number(s) for the author(s) of this article can be found under: https://doi.org/10.

We provide a consistent set of interaction energy curves for the group 2 (IIA) and group 12 (IIB) metal cation/rare gas complexes, M-RG, where M = Be-Ra and Zn-Hg and RG = He-Rn. We report spectroscopic constants derived from these, compare them with available data, and discuss trends in the values. We gain insight into the interactions that occur using a range of approaches: reduced potential energy curves; charge and population analyses; molecular orbital diagrams and contour plots; and Birge-Sponer plots. Although sp hybridization occurs in the Be-RG, Mg-RG and group 12 M-RG complexes, this appears to be minimal and covalency is the main aspect of the interaction. However, major sd hybridization occurs in the heavier group 2 M-RG systems, which increases their interaction energies but there is minimal covalency. Examination of Birge-Sponer plots reveals significant curvature in many cases, which we ascribe to the changing amounts of hybridization or covalency as a function of internuclear separation. This suggests why the use of a simple electrostatics-based model potential to describe the interactions is inadequate.

We report vibrationally-resolved spectra of the S1  S0 transition of chlorobenzene using resonance-enhanced multiphoton ionization (REMPI) spectroscopy. We study chlorobenzene-h5 as well as its perdeuterated isotopologue, chlorobenzene-d5. Changes in the form of the vibrational modes between the isotopologues and also between the S0 and S1 electronic states are discussed for each species. Vibrational bands are assigned utilizing quantum chemical calculations, previous experimental results and isotopic shifts, including those between the 35 Cl and 37 Cl isotopologues. Previous work and assignments of the S1 spectra are discussed. Additionally, the vibrations in the ground state cation, D0 + , are considered, since these have also been used by previous workers in assigning the excited neutral state spectra.

Die intensiv lumineszierenden Chrom(III)-Komplexe [Cr(ddpd) 2 ] 3+ und [Cr(H 2 tpda) 2 ] 3+ zeigen eine überraschende druckinduzierte Rotverschiebung ihrer scharfen Spin-Flip-Emissionsbanden von bis zu À15 cm À1 kbar À1 (ddpd = N,N'-Dimethyl-N,N'-dipyridin-2-yl-pyridin-2,6-diamin; H 2 tpda = 2,6-Bis (2-pyridylamino)pyridin). Diese Verschiebung ist 20-mal stärker als die des etablierten Druckstandards Rubin Al 2 O 3 :Cr 3+ .D ie sehr hohe Quantenausbeute von [Cr-(ddpd) 2 ] 3+ erlaubt zudem sogar optische Druckmessungen in Wasser und Methanol. Diese einzigartigen Merkmale der molekularen Rubine [Cr(ddpd) 2 ] 3+ und [Cr(H 2 tpda) 2 ] 3+ ermçglichen hoch-empfindliche optische Druckmessungen und eine bislang beispiellose Druckmessung mithilfe eines einzigen molekularen Luminophor-Typs.