Luminescence and Light-Driven Energy and Electron Transfer from an Exceptionally Long-Lived Excited State of a Non-Innocent Chromium(III) Complex.

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).

Hybridization and Covalency in the Group 2 and Group 12 Metal Cation/Rare Gas Complexes.

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.

Molecular Ruby under Pressure.

The intensely luminescent chromium(III) complexes [Cr(ddpd)2 ]3+ and [Cr(H2 tpda)2 ]3+ show surprising pressure-induced red shifts of up to -15 cm-1 kbar-1 for their sharp spin-flip emission bands (ddpd=N,N'-dimethyl-N,N'-dipyridine-2-yl-pyridine-2,6-diamine; H2 tpda=2,6-bis(2-pyridylamino)pyridine). These shifts surpass that of the established standard, ruby Al2 O3 :Cr3+ , by a factor of 20. Beyond the common application in the crystalline state, the very high quantum yield of [Cr(ddpd)2 ]3+ enables optical pressure sensing in aqueous and methanolic solution. These unique features of the molecular rubies [Cr(ddpd)2 ]3+ and [Cr(H2 tpda)2 ]3+ pave the way for highly sensitive optical pressure determination and unprecedented molecule-based pressure sensing with a single type of emitter.

Resonance-enhanced multiphoton ionization (REMPI) spectroscopy of bromobenzene and its perdeuterated isotopologue: Assignment of the vibrations of the S(0), S(1), and D(0)(+) states of bromobenzene and the S(0) and D(0)(+) states of iodobenzene.

We report vibrationally resolved spectra of the S1←S0 transition of bromobenzene using resonance-enhanced multiphoton ionization spectroscopy. We study bromobenzene-h5 as well as its perdeuterated isotopologue, bromobenzene-d5. The form of the vibrational modes between the isotopologues and also between the S0 and S1 electronic states is discussed for each species, allowing assignment of the bands to be achieved and the activity between states and isotopologues to be established. Vibrational bands are assigned utilizing quantum chemical calculations, previous experimental results, and isotopic shifts. 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. We also examine the vibrations of iodobenzene in the S0 and D0 (+) states and comment on the previous assignments of these. In summary, we have been able to assign the corresponding vibrations across the whole monohalobenzene series of molecules, in the S0, S1, and D0 (+) states, gaining insight into vibrational activity and vibrational couplings.

HM⁺-RG complexes (M = group 2 metal; RG = rare gas): Physical vs. chemical interactions.

Previous work on the HM(+)-He complexes (M = Be-Ra) has been extended to the cases of the heavier rare gas atoms, HM(+)-RG (RG = Ne-Rn). Optimized geometries and harmonic vibrational frequencies have been calculated using MP2 theory and quadruple-ζ quality basis sets. Dissociation energies for the loss of the rare gas atom have been calculated at these optimized geometries using coupled cluster with single and double excitations and perturbative triples, CCSD(T)theory, extrapolating interaction energies to the basis set limit. Comparisons are made between the present data and the previously obtained helium results, as well as to those of the bare HM(+) molecules; furthermore, comparisons are made to the related M(+)-RG and M(2+)-RG complexes. Partial atomic charge analyses have also been undertaken, and these used to test a simple charge-induced dipole model. Molecular orbital diagrams are presented together with contour plots of the natural orbitals from the quadratic configuration with single and double excitations (QCISD) density. The conclusion is that the majority of these complexes are physically bound, with very little sharing of electron density; however, for M = Be, and to a lesser extent M = Mg, some evidence for chemical effects is seen in HM(+)-RG complexes involving RG atoms with the higher atomic numbers.

Assignment of the vibrations of the S0, S1, and D0 (+) states of perhydrogenated and perdeuterated isotopologues of chlorobenzene.

We report vibrationally resolved spectra of the S1←S0 transition of chlorobenzene using resonance-enhanced multiphoton ionization 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.

Comparison of the interactions in the rare gas hydride and Group 2 metal hydride anions.

We study both the rare gas hydride anions, RG-H(-) (RG = He-Rn) and Group 2 (Group IIa) metal hydride anions, MIIaH(-) (MIIa = Be-Ra), calculating potential energy curves at the CCSD(T) level with augmented quadruple and quintuple basis sets, and extrapolating the results to the basis set limit. We report spectroscopic parameters obtained from these curves; additionally, we study the Be-He complex. While the RG-H(-) and Be-He species are weakly bound, we show that, as with the previously studied BeH(-) and MgH(-) species, the other MIIaH(-) species are strongly bound, despite the interactions nominally also being between two closed shell species: M(ns(2)) and H(-)(1s(2)). We gain insight into the interactions using contour plots of the electron density changes and population analyses. For both series, the calculated dissociation energy is significantly less than the ion/induced-dipole attraction term, confirming that electron repulsion is important in these species; this effect is more dramatic for the MIIaH(-) species than for RG-H(-). Our analyses lead us to conclude that the stronger interaction in the case of the MIIaH(-) species arises from sp and spd hybridization, which allows electron density on the MIIa atom to move away from the incoming H(-).

HM⁺ and HM⁺­He (M = Group 2 metal): chemical or physical interactions?

We investigate the HM(+)­He complexes (M = Group 2 metal) using quantum chemistry. Equilibrium geometries are linear for M = Be and Mg, and bent for M = Ca-Ra; the explanation for this lies in the differing nature of the highest occupied molecular orbitals in the two sets of complexes. The difference primarily occurs as a result of the formation of the H-M(+) bond, and so the HM(+) diatomics are also studied as part of the present work. The position of the He atom in the complexes is largely determined by the form of the electron density. HM(+)…He binding energies are obtained and are surprisingly high for a helium complex. The HBe(+)…He value is almost 3000 cm(-1), which is high enough to suspect contributions from chemical bonding. This is explored by examining the natural orbital density and by population analyses.

Vibrations of the S1 state of fluorobenzene-h5 and fluorobenzene-d5 via resonance-enhanced multiphoton ionization (REMPI) spectroscopy.

We report resonance-enhanced multiphoton ionization spectra of the isotopologues fluorobenzene-h5 and fluorobenzene-d5. 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-d5 observed bands are provided, aided by previous results on fluorobenzene-h5.

Interaction of the NO 3pπ Rydberg state with Ar: potential energy surfaces and spectroscopy.

We present the experimental and simulated (2+1) REMPI spectrum of the C(2)Π state of the NO-Ar complex, in the vicinity of the 3p Rydberg state of NO. Two Rydberg states of NO are expected in this energy region: the C(2)Π (3pπ) and D(2)Σ(+) (3pσ) states, and we concentrate on the former here. When the C(2)Π (3pπ) state interacts with Ar at nonlinear orientations, the symmetry is lowered to C(s), splitting the degeneracy of the (2)Π state to yield C((2)A") and C((2)A') states. For these two states of NO-Ar, we calculate potential energy surfaces using second order Møller-Plesset perturbation theory, exploiting a procedure to converge the reference Hartree-Fock wavefunction to describe the excited states, the maximum overlap method. The bound rovibrational states obtained from the surfaces are used to simulate the electronic spectrum, which is in excellent agreement with experiment, providing assignments for the observed spectral lines from the calculated rovibrational wavefunctions.

Interactions in the B(+)-RG complexes and comparison with Be(+)-RG (RG = He-Rn): evidence for chemical bonding.

Potential energy curves for the interaction of B(+) ((1)S) with RG ((1)S), RG = He-Rn, have been calculated at the CCSD(T) level of theory employing quadruple-ζ and quintuple-ζ quality basis sets. The interaction energies from these curves were subsequently point-by-point extrapolated to the basis set limit. Rovibrational energy levels have been calculated for each extrapolated curve, from which spectroscopic parameters are determined. These are compared to previously determined experimental and theoretical values. The potentials have also been employed to calculate the transport coefficients for B(+) traveling through a bath of RG atoms. We also investigate the interactions between B(+) and the rare gases via contour plots, natural population analysis (NPA), and molecular orbital diagrams. In addition, we consider the atoms-in-molecules (AIM) parameters. The interactions here are compared and contrasted with those for Li(+)-He and Be(+)-RG; it is concluded that there is significant and increasing dative covalent bonding for the Be(+)-RG and B(+)-RG complexes for RG = Ar-Rn, while the other species are predominantly physically bound.

Spectroscopy of the à state of NO-alkane complexes (alkane = methane, ethane, propane, and n-butane).

We have recorded (1+1) resonance-enhanced multiphoton ionization spectra of complexes formed between NO and the alkanes: CH(4), C(2)H(6), C(3)H(8), and n-C(4)H(10). The spectra correspond to the à ← X̃ transition, which is a NO-localized 3s ← 2pπ* transition. In line with previous work, the spectrum for NO-CH(4) has well-defined structure, but this is only partially resolved for the other complexes. The spectra recorded in the NO(+)-alkane mass channels all show a slowly rising onset, followed by a sharp offset, which is associated with dissociation of NO-alkane, from which binding energies in the X̃ and à states are deduced. Beyond this sharp offset, there is a further rise in signal, which is attributed to fragmentation of higher complexes, NO-(alkane)(n). Analysis of these features allows binding energies for (NO-alkane)···alkane to be estimated, and these suggest that in the NO-(alkane)(2) complexes, the second alkane molecule is bound to the first, rather than to NO. Calculated structures for the 1:1 complexes are reported, as well as binding energies.