N-Trityl-2-(tritylsulfan­yl)aniline

The title compound, C44H35NS, is a derivative of amino­thio­phenol and possesses a protected S-triphenyl­methyl thio­ether and an N-triphenyl­methyl­amine functional group. The trityl groups show an anti orientation, with C—C—N—C and C—C—S—C torsion angles of −151.0 (3) and −105.3 (2)°, respectively. There is an intra­molecular N—H⋯S hydrogen bond

2-[2-(Benzyl­sulfan­yl)phen­yl]-1,1,3,3-tetra­methyl­guanidine

The mol­ecular structure of the title compound, C18H23N3S, shows it to be a derivative of an amino­thio­phenol possessing a tetra­methyl­guanidine group with a localized C=N double bond of 1.304 (2) Å and a protected thiol functional group as an S-benzyl thio­ether. The two aromatic ring planes make a dihedral angle of 67.69 (6)°

Unraveling the electrochemical and spectroscopic properties of neutral and negatively charged perylene tetraethylesters

A detailed investigation of the energy levels of perylene-3,4,9,10-tetracarboxylic tetraethylester as a representative compound for the whole family of perylene esters was performed. It was revealed via electrochemical measurements that one oxidation and two reductions take place. The bandgaps determined via the electrochemical approach are in good agreement with the optical bandgap obtained from the absorption spectra via a Tauc plot. In addition, absorption spectra in dependence of the electrochemical potential were the basis for extensive quantum-chemical calculations of the neutral, monoanionic, and dianionic molecules. For this purpose, calculations based on density functional theory were compared with post-Hartree–Fock methods and the CAM-B3LYP functional proved to be the most reliable choice for the calculation of absorption spectra. Furthermore, spectral features found experimentally could be reproduced with vibronic calculations and allowed to understand their origins. In particular, the two lowest energy absorption bands of the anion are not caused by absorption of two distinct electronic states, which might have been expected from vertical excitation calculations, but both states exhibit a strong vibronic progression resulting in contributions to both bands

Fundamental characterization, photophysics and photocatalysis of a base metal iron(II)-cobalt(III) dyad

A new base metal iron-cobalt dyad has been obtained by connection between a heteroleptic tetra-NHC iron(II) photosensitizer combining a 2,6-bis[3-(2,6-diisopropylphenyl)imidazol-2-ylidene]pyridine with 2,6-bis(3-methyl-imidazol-2-ylidene)-4,4′-bipyridine ligand, and a cobaloxime catalyst. This novel iron(II)-cobalt(III) assembly has been extensively characterized by ground- and excited-state methods like X-ray crystallography, X-ray absorption spectroscopy, (spectro-)electrochemistry, and steady-state and time-resolved optical absorption spectroscopy, with a particular focus on the stability of the molecular assembly in solution and determination of the excited-state landscape. NMR and UV/Vis spectroscopy reveal dissociation of the dyad in acetonitrile at concentrations below 1 mM and high photostability. Transient absorption spectroscopy after excitation into the metal-to-ligand charge transfer absorption band suggests a relaxation cascade originating from hot singlet and triplet MLCT states, leading to the population of the $^{3}$MLCT state that exhibits the longest lifetime. Finally, decay into the ground state involves a $^{3}$MC state. Attachment of cobaloxime to the iron photosensitizer increases the $^{3}$MLCT lifetime at the iron centre. Together with the directing effect of the linker, this potentially makes the dyad more active in photocatalytic proton reduction experiments than the analogous two-component system, consisting of the iron photosensitizer and Co(dmgH)$_2$(py)Cl. This work thus sheds new light on the functionality of base metal dyads, which are important for more efficient and sustainable future proton reduction systems

The mixed-valent copper thiolate complex hexakis{μ3-2-[(1,3-dimethylimidazolidene)amino]benzenethiolato}dicopper(II)tetracopper(I) bis(hexafluoridophosphate) acetonitrile disolvate dichloromethane disolvate

The molecular structure of the title compound, [Cu4ICu2II(C11H14N3S)6](PF6)2·2CH3CN·2CH2Cl2, shows a mixed-valent copper(I/II) thiolate complex with a distorted tetrahedral coordination of the CuI and CuII cations by one guanidine N atom and three S atoms each. Characteristic features of the Cu6S6 skeleton are a total of six chemically identical μ3-thiolate bridges and almost planar Cu2S2 units with a maximum deviation of 0.110 (1) Å from the best plane. Each Cu2S2 unit then shares common Cu–S edges with a neighbouring unit; the enclosed dihedral angle is 60.14 (2)°. The geometric centre of the Cu6S6 cation lies on a crystallographic inversion centre. Cu—S bond lengths range from 2.294 (1) to 2.457 (1) Å, Cu—N bond lengths from 2.005 (3) to 2.018 (3) Å and the non-bonding Cu...Cu distances from 2.5743 (7) to 2.5892 (6) Å. C—H...F hydrogen-bond interactions occur between the PF6− anion and the complex molecule and between the PF6− anion and the acetonitrile solvent molecule

2-Benzylsulfanyl-N-(1,3-dimethylimidazolidin-2-ylidene)aniline

The molecular structure of the title compound, C18H21N3S, shows a twisted conformation with a dihedral angle of 67.45 (4)° between the aromatic ring planes and an N—C—C—S torsion angle of −5.01 (13)°. The imidazolidine ring and the aniline moiety make a dihedral angle of 56.03 (4)° and the asscociated C—N—C angle is 125.71 (10)°. The guanidine-like C=N double bond is clearly localized, with a bond length of 1.2879 (14) Å. The C—S—C angle is 102.12 (5)° and the S—C(aromatic) and S—C bond lengths are 1.7643 (11) and 1.8159 (12) Å

Bis(2-{[bis(dimethylamino)methylidene]amino-κN}benzenesulfonato-κN)copper(II)

The molecular structure of the title compound, [Cu(C11H16N3O3S)2], shows the CuII atom with a distorted square-planar coordination geometry from the N2O2 donor set of the two chelating 2-{[bis(dimethylamino)methylidene]amino}benzenesulfonate ligands. The CuII atom lies 0.065 (1) Å above the N2O2 plane and the Cu—O [2 × 1.945 (2) Å] and Cu—N bond lengths [1.968 (3) and 1.962 (3) Å] lie in expected ranges. The two aromatic ring planes make a dihedral angle of 85.48 (1)°