Elucidating the Excited State Behavior of Pyridyl Pyridinium Systems via Computational and Transient Absorption Studies of Tetrahedral Multichromophoric Arrays and their Model Compounds.

The tetrahedral shape-persistent molecule 14+ , containing four identical pyridyl pyridinium units connected via a sp3 hybridized carbon atom, has been investigated in detail by means of steady-state and time resolved spectroscopy. Remarkable photophysical properties are observed, particularly in comparison with protonated and methylated analogues (1H4 8+ , 1Me4 8+ ), which exhibit substantially shorter excited state lifetimes and lower emission quantum yields. Theoretical studies have rationalized the behavior of the tetrameric molecules relative to the monomers, with DFT and TD-DFT calculations corroborating steady-state (absorption and emission) and transient absorption spectra. The behavior of the monomeric compounds (each consisting in one of the four identical subunits of the tetramers, i. e., 2+ , 2H2+ and 2Me2+ ) considerably differs from that of the tetramers, indicating a strong electronic interaction between the subunits in the tetrameric species, likely promoted by the homoconjugation through the connecting sp3  C atom. 2+ is characterized by a peculiar S1 -S2 excited state inversion, whereas the short-lived emitting S1 state of 2H2+ and 2Me2+ exhibits a partial charge-transfer character, as substantiated by spectro-electrochemical studies. Among the six investigated systems, only 14+ is a sizeable luminophore (Φem =0.15), which is related to the peculiar features of its singlet state.

AgX-based hybrid coordination polymers: mechanochemical synthesis, structure and luminescence property characterization.

Hybrid coordination polymers are interesting for their ability to converge the properties of both inorganic and organic systems in one single compound and recently attention has been focused on silver based hybrid coordination polymers due to their luminescence properties. We searched the CSD to establish the propensity of AgXL (X = Cl-, Br- and I-) with L as an organic ligand to form hybrid coordination polymers. About 800 AgXL structures are deposited in the CSD, with huge structural variability: indeed, it is possible to recognize some structural preferences based on the halide nature. The formation of an inorganic polymeric unit is favoured by iodide but it is also possible with the other halides. This research continues with the synthesis of AgX (X = I-, Br-) based coordination polymers with 2-, 3- and 4-picolylamine (n-pica) as ligands. By mechanochemical synthesis five new hybrid coordination polymers and one coordination polymer have been obtained and their structures determined. While [(AgI)(n-pica)]n are not luminescent, [(AgBr)(n-pica)]n emit and their profile depends on the crystallinity of the sample.

Novel Cu(I)-5-nitropyridine-2-thiol Cluster with NIR Emission: Structural and Photophysical Characterization.

A novel Cu(I) cluster compound has been synthesized by reacting CuI with the 2,2'-dithiobis(5-nitropyridine) ligand under solvothermal conditions. During the reaction, the original ligand breaks into the 5-nitropyridine-2-thiolate moiety, which acts as the coordinating ligand with both N- and S-sites, leading to a distorted octahedral Cu6S6 cluster. The structure has been determined by single-crystal X-ray diffraction and FT-IR analysis, and the photophysical properties have been determined in the solid state by means of steady-state and time-resolved optical techniques. The cluster presents a near-infrared emission showing an unusual temperature dependence: when passing from 77 to 298 K, a blue-shift of the emission band is observed, associated with a decrease in its intensity. Time-dependent-density functional theory calculations suggest that the observed behavior can be ascribed to a complex interplay of excited states, basically in the triplet manifold.

Exploring the ancient chemistry of mercury.

This paper explores the chemistry of mercury as described in ancient alchemical literature. Alchemy's focus on the knowledge and manipulation of natural substances is not so different from modern chemistry's purposes. The great divide between the two is marked by the way of conceptualizing and recording their practices. Our interdisciplinary research group, composed of chemists and historians of science, has set off to explore the cold and hot extraction of mercury from cinnabar. The ancient written records have been perused in order to devise laboratory experiments that could shed light on the material reality behind the alchemical narratives and interpret textual details in a unique perspective. In this way, it became possible to translate the technical lore of ancient alchemy into the modern language of chemistry. Thanks to the replication of alchemical practices, chemistry can regain its centuries-long history that has fallen into oblivion.

Boosting Gold(I) Catalysis via Weak Interactions: New Fine-Tunable Impy Ligands.

A series of modular ImPy-carbene-Au(I) complexes are synthesized and fully characterized both in the solid state and in solution. The presence of oligoaryl units (phenyl and thienyl rings) at the C5-position of the ImPy core (in close proximity to the gold center) imprints on the organometallic species fine-tunable and predictable catalytic properties. A marked accelerating effect was recorded in several [Au(I)]-catalyzed electrophilic activations of unsaturated hydrocarbons when a CF3-containing aromatic ring was accommodated at the ImPy core.

Understanding the mechanism of direct visible-light-activated [2 + 2] cycloadditions mediated by Rh and Ir photocatalysts: combined computational and spectroscopic studies.

The mechanism of [2 + 2] cycloadditions activated by visible light and catalyzed by bis-cyclometalated Rh(iii) and Ir(iii) photocatalysts was investigated, combining density functional theory calculations and spectroscopic techniques. Experimental observations show that the Rh-based photocatalyst produces excellent yield and enantioselectivity whereas the Ir-photocatalyst yields racemates. Two different mechanistic features were found to compete with each other, namely the direct photoactivation of the catalyst-substrate complex and outer-sphere triplet energy transfer. Our integrated analysis suggests that the direct photocatalysis is the inner working of the Rh-catalyzed reaction, whereas the Ir catalyst serves as a triplet sensitizer that activates cycloaddition via an outer-sphere triplet excited state energy transfer mechanism.

Giant Shape-Persistent Tetrahedral Porphyrin System: Light-Induced Charge Separation.

Tetraphenylmethane appended with four pyridylpyridinium units works as a scaffold to self-assemble four ruthenium porphyrins in a tetrahedral shape-persistent giant architecture. The resulting supramolecular structure has been characterised in the solid state by X-ray single crystal analysis and in solution by various techniques. Multinuclear NMR spectroscopy confirms the 1 : 4 stoichiometry with the formation of a highly symmetric structure. The self-assembly process can be monitored by changes of the redox potentials, as well as by modifications in the visible absorption spectrum of the ruthenium porphyrin and by a complete quenching of both the bright fluorescence of the tetracationic scaffold and the weak phosphorescence of the ruthenium porphyrin. An ultrafast photoinduced electron transfer is responsible for this quenching process. The lifetime of the resulting charge separated state (800 ps) is about four times longer in the giant supramolecular structure compared to the model 1 : 1 complex formed by the ruthenium porphyrin and a single pyridylpyridinium unit. Electron delocalization over the tetrameric pyridinium structure is likely to be responsible for this effect.

A supramolecular bifunctional iridium photoaminocatalyst for the enantioselective alkylation of aldehydes.

The construction of a hybrid metal-organo-photoredox catalyst based on the conjugation of an imidazolidinone organocatalyst and Ir(ppy)2(bipy) (ppy = 2-phenylpyridine, bipy = bipyridine) is described. The introduction of the desired organocatalyst into the bipyridine moiety is quite modular, allowing the preparation of different hybrid photocatalysts, and is realized though a simple click reaction. The hybrid photocatalysts obtained were employed in the benchmark photoredox alkylation of aldehydes. Remarkably, the conjugation of a first-generation MacMillan catalyst produces an active and stereoselective hybrid photoredox catalyst.

Allylation of aldehydes by dual photoredox and nickel catalysis.

Here we report the application of dual nickel/photoredox catalysis to the allylation of aliphatic, aromatic and heteroaromatic aldehydes by using commercially available reagents. The process utilizes the combination of a Ni(ii) complex, [Ru(bpy)3]2+ as a photoredox catalyst, and allylacetate under blue LED irradiation, and allows the synthesis of a large variety of homoallylic alcohols.

Application of coumarin dyes for organic photoredox catalysis.

Here we report the application of readily prepared and available coumarin dyes for photoredox catalysis, which are able to mimic powerful reductant [Ir(iii)] complexes. Coumarin derivatives 9 and 10 were employed as photoreductants in pinacol coupling and in other reactions, in the presence of Et3N as a sacrificial reducing agent. As the electronic, photophysical, and steric properties of coumarins could be varied, a wide applicability to several classes of photoredox reactions is predicted.

Mechanistic insights into two-photon-driven photocatalysis in organic synthesis.

A mechanism based on the sequential absorption of two photons by the components of a redox couple has been recently proposed for catalysis of the energetically demanding reduction of aryl halides. Here, we analyze the suggested photochemical mechanism of this reaction, which employs perylenediimide (PDI) as a photocatalyst, on the basis of spectroscopic, electrochemical and electron paramagnetic resonance data. Our results indicate that the photoexcited PDI radical anion (*PDI˙-) cannot play the role of a photosensitizer in the aforementioned process. Instead, the reduction of 4'-bromoacetophenone likely involves *PDI˙- decomposition products. The extremely short lifetime of the photoexcited transient species, as *PDI˙-, is a major general limitation for photocatalytic schemes based on sequential two-photon excitation. In order to better understand the potential of such schemes, we discuss them in the context of the Z-scheme in natural photosynthesis.

Asymmetric [3+2] Photocycloadditions of Cyclopropanes with Alkenes or Alkynes through Visible-Light Excitation of Catalyst-Bound Substrates.

The herein reported visible-light-activated catalytic asymmetric [3+2] photocycloadditions between cyclopropanes and alkenes or alkynes provide access to chiral cyclopentanes and cyclopentenes, respectively, in 63-99 % yields and with excellent enantioselectivities of up to >99 % ee. The reactions are catalyzed by a single bis-cyclometalated chiral-at-metal rhodium complex (2-8 mol %) which after coordination to the cyclopropane generates the visible-light-absorbing complex, lowers the reduction potential of the cyclopropane, and provides the asymmetric induction and overall stereocontrol. Enabled by a mild single-electron-transfer reduction of directly photoexcited catalyst/substrate complexes, the presented transformations expand the scope of catalytic asymmetric photocycloadditions to simple mono-acceptor-substituted cyclopropanes affording previously inaccessible chiral cyclopentane and cyclopentene derivatives.

Photoredox Catalysis: The Need to Elucidate the Photochemical Mechanism.

The photocatalytic mechanism reported in a recent Communication to produce the radical anion of pyrenes postulates a highly endergonic electron transfer process. An analysis of the thermodynamics is reported together with the proposal of an alternative thermodynamically feasible mechanism.

Hierarchical Growth of Supramolecular Structures Driven by Pimerization of Tetrahedrally Arranged Bipyridinium Units.

A shape-persistent molecule, featuring four bipyridinium units, has been synthesized that upon reduction undergoes intermolecular pimerization because of the rigid architecture of the molecule. The pimerization process has been investigated by a variety of techniques, such as absorption measurements, EPR spectroscopy, as well as gamma and pulse radiolysis, and compared with the behavior of a model compound. Computational studies have also been performed to support the experimental data. The most interesting feature of the tetramer is that pimerization occurs only above a threshold concentration of monoreduced species, on the contrary to the model compound. Furthermore, there is an increase of the apparent pimerization constant by increasing the concentration of reduced bipyridinium units. These results have been interpreted by the fact that pimerization is favored in the tetrahedrally shaped molecule because of a cooperative mechanism. Each multiply reduced molecule can indeed undergo multiple intermolecular interactions that enhance the stabilization of the system, also leading to hierarchical supramolecular growth. The resulting supramolecular system formed by such intermolecular pimerization should exhibit a diamond-like structure, as suggested by a simplified modeling approach. The intermolecular nature of the pimerization process occurring in the tetramer has been demonstrated by measuring the corresponding bimolecular rate constant by pulsed radiolysis experiments.

Visible-Light-Induced Direct Photocatalytic Carboxylation of Indoles with CBr4 /MeOH.

Photocatalysis enables the cascade reactions of indoles and CBr4 in MeOH through a C(sp(2) )H functionalization/methanolysis sequence. The title reaction provides an efficient access to indole 2- and 3-carboxylates in a single operation (no preinstallation of protecting as well as directing groups was required) with good yields under mild reaction conditions.

A highly luminescent tetramer from a weakly emitting monomer: acid- and redox-controlled multiple complexation by cucurbit[7]uril.

The tetrahedral, shape-persistent molecule 1(4+), containing four pyridylpyridinium units connected through a central carbon atom, exhibits unexpected photophysical properties including a substantially redshifted absorption (2350 cm(-1)) and a very strong fluorescence (Φem = 40 %), compared with the monomer 2(+) (Φem = 0.4 %). Density functional theory calculations on the structure and spectroscopic properties of 1(4+) and 2(+) show that exciton interactions, homoconjugation, and orbital nature account for the observed differences in their photophysical properties. The protonated tetramer binds four cucurbit[7]uril molecules and the host/guest interactions can be controlled by chemical (acid/base) as well as redox stimuli.

Rotational spectrum and internal dynamics of tetrahydrofuran-krypton.

The rotational spectrum of the tetrahydrofuran-krypton van der Waals complex has been investigated by pulsed-jet Fourier transform microwave spectroscopy. The spectra of the (84)Kr and (86)Kr isotopologues have been assigned and the krypton atom is located nearly over the oxygen atom, almost perpendicular to the COC plane. Each rotational transition is split into two component lines due to, according to the observed Coriolis coupling term between the tunneling states, the residual pseudorotational effects of the ring in the complex. The splitting between the two vibrational sublevels is 87.462(2) and 87.062(2) MHz for the (84)Kr and (86)Kr isotopologues, respectively. These splittings have been used to determine the barrier to inversion, B(2) = 67 cm(-1). The dissociation energy has been estimated to be 3.7 kJ mol(-1) from centrifugal distortion effects.