A Combined Spectroscopic and Theoretical Study on a Ruthenium Complex Featuring a π-Extended dppz Ligand for Light-Driven Accumulation of Multiple Reducing Equivalents.

The design of photoactive systems capable of storing and relaying multiple electrons is highly demanded in the field of artificial photosynthesis, where transformations of interest rely on multielectronic redox processes. The photophysical properties of the ruthenium photosensitizer [(bpy) Ru(oxim-dppqp)] (Ru), storing two electrons coupled to two protons on the π-extended oxim-dppqp ligand under light-driven conditions, are investigated by means of excitation wavelength-dependent resonance Raman and transient absorption spectroscopies, in combination with time-dependent density functional theory; the results are discussed in comparison to the parent [(bpy) Ru(dppz)] and [(bpy) Ru(oxo-dppqp)] complexes. In addition, this study provides in-depth insights on the impact of protonation or of accumulation of multiple reducing equivalents on the reactive excited states.

Tuning the Electron Storage Potential of a Charge-Photoaccumulating Ru Complex by a DFT-Guided Approach.

Molecular photosensitizers that are able to store multiple reducing equivalents are of great interest in the field of solar fuel production, where most reactions involve multielectronic reduction processes. In order to increase the reducing power of a ruthenium tris-diimine charge-photoaccumulating complex, two structural modifications on its fused dipyridophenazine-pyridoquinolinone ligand were computationally investigated. Addition of an electron-donating oxime group was calculated to substantially decrease the reduction potentials of the complex, thus guiding the synthesis of a pyridoquinolinone-oxime derivative.

Recent Advances in Isoindigo-Inspired Organic Semiconductors.

Over the past decade, isoindigo has become a widely used electron-deficient subunit in donor-acceptor organic semiconductors, and these isoindigo-based materials have been widely used in both organic photovoltaic (OPV) devices and organic field effect transistors (OFETs). Shortly after the development of isoindigo-based semiconductors, researchers began to modify the isoindigo structure in order to change the optoelectronic properties of the resulting materials. This led to the development of many new isoindigo-inspired compounds; since 2012, the Kelly Research Group has synthesized a number of these isoindigo analogues and produced a variety of new donor-acceptor semiconductors.

Lewis Acid-Base Chemistry of 7-Azaisoindigo-Based Organic Semiconductors.

Low-band-gap organic semiconductors are important in a variety of organic electronics applications, such as organic photovoltaic devices, photodetectors, and field effect transistors. Building on our previous work, which introduced 7-azaisoindigo as an electron-deficient building block for the synthesis of donor-acceptor organic semiconductors, we demonstrate how Lewis acids can be used to further tune the energies of the frontier molecular orbitals. Coordination of a Lewis acid to the pyridinic nitrogen of 7-azaisoindigo greatly diminishes the electron density in the azaisoindigo π-system, resulting in a substantial reduction in the lowest unoccupied molecular orbital (LUMO) energy.

Self-assembled Ln(III)4 (Ln = Eu, Gd, Dy, Ho, Yb) [2 × 2] square grids: a new class of lanthanide cluster.

Self-assembly of the Ln(III) ions (Ln = Eu, Gd, Dy, Ho, Yb) into square [2 × 2] grid-like arrays has been readily effected using simple, symmetric ditopic ligands based on a carbohydrazone core. The metal ions are connected via single atom bridges (e.g.

6,6'-Dimeth-oxy-2,2'-{[(E,E)-hydrazine-1,2-diyl-idene]bis-(methanylyl-idene)}diphenol methanol disolvate.

The title compound, C(16)H(16)N(2)O(4)·2CH(3)OH, is a hydrazone in an E geometric arrangement, with an inversion centre at the mid-point of the N-N bond. A symmetry-related pair of six-membered hydrogen-bonded rings [graph-set motif S(1) (1)(6)] are present for the terminal vanillin-imine moieties. Two lattice methanol solvent mol-ecules are present per formula unit (Z' = 1/2), which form hydrogen-bonded chains along [010] with two orientations due to disorder of the methanol H-atom.

Primary fragmentation pathways of gas phase [M(uracil-H)(uracil)]+ complexes (M=Zn, Cu, Ni, Co, Fe, Mn, Cd, Pd , Mg, Ca, Sr, Ba, and Pb): loss of uracil versus HNCO.

Complexes formed between metal dications, the conjugate base of uracil, and uracil are investigated by sustained off-resonance irradiation collision-induced dissociation (SORI-CID) in a Fourier transform ion cyclotron resonance (FTICR) mass spectrometer. Positive-ion electrospray spectra show that [M(Ura-H)(Ura)](+) (M=Zn, Cu, Ni, Co, Fe, Mn, Cd, Pd, Mg, Ca, Sr, Ba, or Pb) is the most abundant ion even at low concentrations of uracil. SORI-CID experiments show that the main primary decomposition pathway for all [M(Ura-H)(Ura)](+) , except where M=Ca, Sr, Ba, or Pb, is the loss of HNCO.