Where Does the Proton Go? Structure and Dynamics of Hydrogen-Bond Switching in Aminophosphine Chalcogenides.

Aminophosphates are the focus of research on prebiotic phosphorylation chemistry. Their bifunctional nature also makes them a powerful class of organocatalysts. However, the structural chemistry and dynamics of proton-binding in phosphorylation and organocatalytic mechanisms are still not fully understood.

Mechanistic insights into the visible-light-driven -arylation of carboxylic acids catalyzed by xanthine-based nickel complexes.

We present a photocatalytic protocol for the -arylation of carboxylic acids using nickel complexes bearing C8-pyridyl xanthines. Our studies suggest that the underlying mechanism operates independently of external photosensitizers. Stoichiometric experiments and crystallographic studies characterize the catalytically relevant Ni complexes.

A dual experimental-theoretical perspective on ESPT photoacids and their challenges ahead.

Photoacids undergo an increase in acidity upon electronic excitation, enabling excited-state proton transfer (ESPT) reactions. A multitude of compounds that allow ESPT has been identified and integrated in numerous applications, as is outlined by reviewing the rich history of photoacid research reaching back more than 90 years. In particular, achievements together with ambitions and challenges are highlighted from a combined experimental and theoretical perspective.

Asymmetric Migratory Tsuji-Wacker Oxidation Enables the Enantioselective Synthesis of Hetero- and Isosteric Diarylmethanes.

Diarylmethanes play, in part, a pivotal role in the design of highly potent, chiral, nonracemic drugs whose bioactivity is typically affected by the substitution pattern of their arene units. In this context, certain arenes such as -substituted benzenes or unsubstituted heteroarenes cause particular synthetic challenges, since such isosteric residues at the central methane carbon atom are typically indistinguishable for a chiral catalyst. Hence, the stereoselective incorporation of isosteric (hetero)arenes into chiral methane scaffolds requires the use of stoichiometrically differentiated building blocks, which is typically realized through preceding redox-modifying operations such as metalation or halogenation and thus associated with disadvantageous step- and redox-economic traits.

Fluorescent probes for investigating the internalisation and action of bioorthogonal ruthenium catalysts within Gram-positive bacteria.

Bioorthogonal reactions are extremely useful for the chemical modification of biomolecules, and are already well studied in mammalian cells. In contrast, very little attention has been given to the feasibility of such reactions in bacteria. Herein we report modified coumarin dyes for monitoring the internalisation and activity of bioorthogonal catalysts in the Gram-positive bacterial species .

Tuning The Intracellular Distribution of [3+2+1] Iridium(III) Complexes In Bacterial And Mammalian Cells By iClick Reaction With Biomolecular Carriers Functionalized With Alkynone Groups.

Three iridium(III) triazolato complexes of the general formula [Ir(triazolato)(ppy)(terpy)]PF with ppy=2-phenylpyridine and terpy=2,2':6',2''-terpyridine were efficiently prepared by iClick reaction of [Ir(N)(ppy)(terpy)]PF, with alkynes and alkynones, which allowed facile introduction of biological carriers such as biotin and cholic acid. In contrast to the precursor azido complex, which decomposed upon photoexcitation on a very short time scale, the triazolato complexes were stable in solution for up to 48 h. They emit in the spectral region around 540 nm with a quantum yield of 15-35 % in aerated acetonitrile solution and exhibit low cytotoxicity with IC values >50 μM for most complexes in L929 and HeLa cells, demonstrating their high suitability as luminescent probes.

Unimolecular net heterolysis of symmetric and homopolar σ-bonds.

The unimolecular heterolysis of covalent σ-bonds is integral to many chemical transformations, including S1-, E1- and 1,2-migration reactions. To a first approximation, the unequal redistribution of electron density during bond heterolysis is governed by the difference in polarity of the two departing bonding partners. This means that if a σ-bond consists of two identical groups (that is, symmetric σ-bonds), its unimolecular fission from the S, S, or T states only occurs homolytically after thermal or photochemical activation.

Cobalt-Mediated Photochemical C-H Arylation of Pyrroles.

Precious metal complexes remain ubiquitous in photoredox catalysis (PRC) despite concerted efforts to find more earth-abundant catalysts and replacements based on 3d metals in particular. Most otherwise plausible 3d metal complexes are assumed to be unsuitable due to short-lived excited states, which has led researchers to prioritize the pursuit of longer excited-state lifetimes through careful molecular design. However, we report herein that the C-H arylation of pyrroles and related substrates (which are benchmark reactions for assessing the efficacy of photoredox catalysts) can be achieved using a simple and readily accessible octahedral bis(diiminopyridine) cobalt complex, [1-Co](PF).

Structure and photochemistry of di--butyldiphosphatetrahedrane.

Di--butyldiphosphatetrahedrane (BuCP) (1) is a mixed carbon- and phosphorus-based tetrahedral molecule, isolobal to white phosphorus (P). However, despite the fundamental significance and well-explored reactivity of the latter molecule, the precise structure of the free (BuCP) molecule (1) and a detailed analysis of its electronic properties have remained elusive. Here, single-crystal X-ray structure determination of 1 at low temperature confirms the tetrahedral structure.

Reactivity of Superbasic Carbanions Generated via Reductive Radical-Polar Crossover in the Context of Photoredox Catalysis.

Photocatalytic reactions involving a reductive radical-polar crossover (RRPCO) generate intermediates with carbanionic reactivity. Many of these proposed intermediates resemble highly reactive organometallic compounds. However, conditions of their formation are generally not tolerated by their isolated organometallic versions and often a different reactivity is observed.

Creating a Defined Chirality in Amino Acids and Cyclic Dipeptides by Photochemical Deracemization.

2,5-Diketopiperazines are cyclic dipeptides displaying a wide range of applications. Their enantioselective preparation has now been found possible from the respective racemates by a photochemical deracemization (53 examples, 74 % to quantitative yield, 71-99 % ee). A chiral benzophenone catalyst in concert with irradiation at λ=366 nm enables to establish the configuration at the stereogenic carbon atom C6 at will.

Multifaceted View on the Mechanism of a Photochemical Deracemization Reaction.

Upon irradiation in the presence of a chiral benzophenone catalyst (5 mol %), a racemic mixture of a given chiral imidazolidine-2,4-dione (hydantoin) can be converted almost quantitatively into the same compound with high enantiomeric excess (80-99% ). The mechanism of this photochemical deracemization reaction was elucidated by a suite of mechanistic experiments. It was corroborated by nuclear magnetic resonance titration that the catalyst binds the two enantiomers by two-point hydrogen bonding.

Wavelength-dependent photochemistry of a salicylimine derivative studied with cryogenic and ultrafast spectroscopy approaches.

Salicylimines are versatile compounds in which an excited-state intramolecular proton transfer and torsional motions may set in upon photoexcitation. Here, we study -(α-phenylethyl)salicylimine (PESA) to elucidate how the photochemical reaction pathways depend on the excitation wavelength and to what extent the relative photoproduct distribution can be steered towards a desired species. DFT structure and potential energy calculations disclose that the most stable ground-state conformer is an enol species and that the photodynamics may proceed differently depending on the excited state that is reached.

Monitoring the photochemistry of a formazan over 15 orders of magnitude in time.

2,3,5-triphenyltetrazolium chloride (TTC) may convert into phenyl-benzo[c]tetrazolocinnolium chloride (PTC) and 1,3,5-triphenylformazan (TPF) under irradiation with light. The latter reaction, albeit enzymatically rather than photochemically, is used in so-called TTC assays indicating cellular respiration and cell growth. In this paper, we address the photochemistry of TPF with time-resolved spectroscopy on various time scales.

Ultrafast transient absorption and solvation of a super-photoacid in acetoneous environments.

The phenomenon of photoacidity, i.e., an increase in acidity by several orders of magnitude upon electronic excitation, is frequently encountered in aromatic alcohols capable of transferring a proton to a suitable acceptor.

Steering the Ultrafast Opening and Closure Dynamics of a Photochromic Coordination Cage by Guest Molecules.

Photochemical studies on supramolecular hosts that can encapsulate small guest molecules commonly focus on three aspects: photoswitching the cage to release or trap the guest, the effect of the confining environment on the guest, and light-induced exciton or charge transfer within the cage structure. Here, we exploit ultrafast spectroscopy to address how the guest alters the photoswitching characteristics of the cage. For this, the impacts of three disparate guest compounds on ring-opening or ring-closure of a dithienylethene (DTE) ligand in a photoswitchable DTE-based coordination cage are juxtaposed.

Hydrogen-Bond-Modulated Nucleofugality of Se Species to Enable Photoredox-Catalytic Semipinacol Manifolds.

Chemical bond activations mediated by H-bond interactions involving highly electronegative elements such as nitrogen and oxygen are powerful tactics in modern catalysis research. On the contrary, kindred catalytic regimes in which heavier, less electronegative elements such as selenium engage in H-bond interactions to co-activate C-Se σ-bonds under oxidative conditions are elusive. Traditional strategies to enhance the nucleofugality of selenium residues predicate on the oxidative addition of electrophiles onto Se -centers, which entails the elimination of the resulting Se moieties.

Pseudo-Octahedral Iron(II) Complexes with Near-Degenerate Charge Transfer and Ligand Field States at the Franck-Condon Geometry.

Increasing the metal-to-ligand charge transfer (MLCT) excited state lifetime of polypyridine iron(II) complexes can be achieved by lowering the ligand's π* orbital energy and by increasing the ligand field splitting. In the homo- and heteroleptic complexes [Fe(cpmp) ] (1 ) and [Fe(cpmp)(ddpd)] (2 ) with the tridentate ligands 6,2''-carboxypyridyl-2,2'-methylamine-pyridyl-pyridine (cpmp) and N,N'-dimethyl-N,N'-di-pyridin-2-ylpyridine-2,6-diamine (ddpd) two or one dipyridyl ketone moieties provide low energy π* acceptor orbitals. A good metal-ligand orbital overlap to increase the ligand field splitting is achieved by optimizing the octahedricity through CO and NMe units between the coordinating pyridines which enable the formation of six-membered chelate rings.

Sensitivity of Isomerization Kinetics of 1,3,5-Triphenylformazan on Cosolvents Added to Toluene.

Formazan molecules exhibit photochromism because isomerization processes following excitation may occur in both the azo group and the hydrazone group; thus, each formazan may be present in various forms with different colors. The ratio of these forms depends on the illumination conditions and the environment of the formazan with a most incisive sensibility of the thermal relaxation of the C═N toward slight traces of impurities in toluene solutions, as reported most prominently for 1,3,5-triphenylformazan. Here, we study the latter compound with transient absorption spectroscopy to investigate the role of these traces by adding small amounts of both protic and aprotic cosolvents.

Ultrafast photochemistry of a molybdenum carbonyl-nitrosyl complex with a triazacyclononane coligand.

Transition metal complexes capable of releasing small molecules such as carbon monoxide and nitric oxide upon photoactivation are versatile tools in various fields of chemistry and biology. In this work, we report on the ultrafast photochemistry of [Mo(CO)(NO)(Prtacn)]PF (Prtacn = 1,4,7-triisopropyl-1,4,7-triazacyclononane), which was characterized under continuous illumination and with femtosecond UV-pump/UV-probe and UV-pump/MIR-probe spectroscopy, as well as with stationary calculations. The experimental and theoretical results demonstrate that while the photodissociation of one of the two CO ligands upon UV excitation can be inferred both on an ultrafast timescale as well as under exposure times of several minutes, no evidence of NO release is observed under the same conditions.

Ionic Liquids [M ][A ] with Three-Valent Cations and Their Possible Use to Easily Separate Rare Earth Metals.

We introduce a simple way to liquify rare earth metals (REM) by incorporating the corresponding cations, in particular Eu , La , and Y , into polyvalent ionic liquids (ILs). In contrast to conventional methods, this is achieved not by transforming them into anionic complexes, but by keeping them as bare cations and combining them with convenient, cheap and commercially available anions (A) in the form [REM ][A ] . To do so, we follow the COncept of Melting Point Lowering due to EThoxylation (COMPLET) with alkyl polyethylene oxide carboxylates as anions.

Tracing absorption and emission characteristics of halogen-bonded ion pairs involving halogenated imidazolium species.

We investigate how the absorption and fluorescence of halogenated imidazolium compounds in acetonitrile solution is influenced by the presence of counterions and the ability to act as halogen-bond donors. Experimental measurements and quantum chemical calculations with correlated wavefunction methods are applied to study three monodentate halogen-bond complexes of iodo-imidazolium, iodo-benzimidazolium and bromo-benzimidazolium cations with triflate counterions, and a bidentate complex of bis(iodo-benzimidazolium) dications with chloride as counterion. The three monodentate complexes with triflate counterions relax after photoexcitation to minima on the S potential energy surface where the C-I bond and the IO halogen bond are partially broken.

Thermodynamic driving forces of guest confinement in a photoswitchable cage.

Photoswitchable cages that confine small guest molecules inside their cavities offer a way to control the binding/unbinding process through irradiation with light of different wavelengths. However, detailed characterization of the structural and thermodynamic consequences of photoswitching is very challenging to achieve by experiments alone. Thus, all-atom molecular dynamics (MD) simulations were carried out to gain insight into the relationship between the structure and binding affinity.

Unveiling Luminescent Ir and Rh N-Heterocyclic Carbene Complexes: Structure, Photophysical Specifics, and Cellular Localization in the Endoplasmic Reticulum.

Complexes of Rh and Ir of the [M(COD)(NHC)X] type (where M=Rh or Ir, COD=1,5-cyclooctadiene, NHC=N-heterocyclic carbene, and X=halide) have recently shown promising cytotoxic activities against several cancer cell lines. Initial mechanism of action studies provided some knowledge about their interaction with DNA and proteins. However, information about their cellular localization remains scarce owing to luminescence quenching within this complex type.

Extended Hydrogen Bond Networks for Effective Proton-Coupled Electron Transfer (PCET) Reactions: The Unexpected Role of Thiophenol and Its Acidic Channel in Photocatalytic Hydroamidations.

Preorganization and aggregation in photoredox catalysis can significantly affect reactivities or selectivities but are often neglected in synthetic and mechanistic studies, since the averaging effect of flexible ensembles can effectively hide the key activation signatures. In addition, aggregation effects are often overlooked due to highly diluted samples used in many UV studies. One prominent example is Knowles's acceleration effect of thiophenol in proton-coupled electron transfer mediated hydroamidations, for which mainly radical properties were discussed.