Unexpected Redox Chemistry of P∩N- and As∩N-Rhenium(I) Tricarbonyl Complexes in the Presence of CO2 Acting as an Acid.

This study reports on Re tricarbonyl complexes bearing 8-(diphenylphosphanyl)quinoline, P∩N, and 8-(diphenylarsanyl)quinoline, As∩N, as bidendate ligands. We studied the reactivity of these complexes in comparison with fac-Re(N∩N)(CO)3Cl (with N∩N = 2,2'-bipyridine or 4,4'-dimethyl-2,2'-bipyridine). We used a combination of electrochemical and spectroelectrochemical methods with time-resolved spectroscopy over 10 orders of magnitude (100 ps-1 s) to investigate the peculiar reactivity of one-electron-reduced Re(CO)3(P∩N)Cl and Re(CO)3(As∩N)Cl complexes also in the presence of protons.

Cooperative Chiral Lewis Base/Palladium-Catalyzed Asymmetric Syntheses of Methylene-Containing δ-Lactams.

We herein report a two-step approach for the enantioselective synthesis of novel chiral δ-lactams. By using a cooperative chiral ITU/achiral Pd-catalyst system, this protocol proceeds via an asymmetric α-allylation of activated aryl esters first, followed by an acid-mediated lactam formation. A variety of differently substituted products could be obtained with usually high levels of enantioselectivities and in reasonable yields (16 examples, up to 98 : 2 er and 73 % yield over two steps). In addition, further utilizations of the products via transformations of the exocyclic double bond were successfully carried out as well.

Noncovalent Synergy: Aurophilicity and Aryl Stacking in Bis(gold(I)aryl)-dmpm Complexes.

Bis(dimethylphosphino)methane (dmpm) was used as a ligand to synthesize four semi-supported dinuclear gold(I) complexes, dmpm(AuR)2 (R = Cl, C6H5, C6Cl5, and C6F5), which were studied concerning the synergistic effects of two weak noncovalent interactions: aurophilic and aryl-aryl stacking interactions. The chloro-substituted complex was synthesized by the ligand substitution of (tht)AuCl with dmpm and further functionalized by the reaction with PhMgBr or in situ-generated C6Cl5Li to afford the phenyl- and pentachlorophenyl-substituted compounds, respectively. The pentafluorophenyl-substituted gold complex was generated by the ligand substitution of (tht)Au(C6F5) with dmpm. All complexes were characterized by multinuclear NMR spectroscopy, CHN analyses, and X-ray diffraction experiments. Additionally, the basic photoluminescence properties of dmpm(AuCl)2, dmpm(AuC6Cl5)2, and dmpm(AuC6F5)2 were examined. The aggregation behavior of dmpm(AuC6F5)2 was further investigated by variable-temperature diffusion-ordered NMR spectroscopy experiments.

Enantioselective organocatalytic syntheses of α-selenated α- and ß-amino acid derivatives.

Selenium-containing amino acids are valuable targets but methods for the stereoselective α-selenation of simple amino acid precursors are rare. We herein report the enantioselective electrophilic α-selenation of azlactones (masked α-amino acid derivatives) and isoxazolidin-5-ones (masked ß-amino acids) using Cinchona alkaloids as easily accessible organocatalysts. A variety of differently substituted derivatives was accessed with reasonable levels of enantioselectivities and further studies concerning the stability and suitability of these compounds for further manipulations have been carried out as well.

P∩N Bridged Cu(I) Dimers Featuring Both TADF and Phosphorescence. From Overview towards Detailed Case Study of the Excited Singlet and Triplet States.

We present an overview over eight brightly luminescent Cu(I) dimers of the type Cu2X2(P∩N)3 with X = Cl, Br, I and P∩N = 2-diphenylphosphino-pyridine (Ph2Ppy), 2-diphenylphosphino-pyrimidine (Ph2Ppym), 1-diphenylphosphino-isoquinoline (Ph2Piqn) including three new crystal structures (Cu2Br2(Ph2Ppy)3 1-Br, Cu2I2(Ph2Ppym)3 2-I and Cu2I2(Ph2Piqn)3 3-I). However, we mainly focus on their photo-luminescence properties. All compounds exhibit combined thermally activated delayed fluorescence (TADF) and phosphorescence at ambient temperature. Emission color, decay time and quantum yield vary over large ranges. For deeper characterization, we select Cu2I2(Ph2Ppy)3, 1-I, showing a quantum yield of 81%. DFT and SOC-TDDFT calculations provide insight into the electronic structures of the singlet S1 and triplet T1 states. Both stem from metal+iodide-to-ligand charge transfer transitions. Evaluation of the emission decay dynamics, measured from 1.2 ≤ T ≤ 300 K, gives ∆E(S1-T1) = 380 cm-1 (47 meV), a transition rate of k(S1→S0) = 2.25 × 106 s-1 (445 ns), T1 zero-field splittings, transition rates from the triplet substates and spin-lattice relaxation times. We also discuss the interplay of S1-TADF and T1-phosphorescence. The combined emission paths shorten the overall decay time. For OLED applications, utilization of both singlet and triplet harvesting can be highly favorable for improvement of the device performance.

Dynamic Supramolecular Ruthenium-Based Gels Responsive to Visible/NIR Light and Heat.

A simple supramolecular crosslinked gel is reported with a photosensitive ruthenium bipyridine complex functioning as a crosslinker and poly(4-vinylpyridine) (P4VP) as a macromolecular ligand. Irradiation of the organogels in H2 O/MeOH with visible and NIR light (in a multiphoton process) leads to cleavage of pyridine moieties from the ruthenium complex breaking the cross-links and causing degelation and hence solubilization of the P4VP chains. Real-time (RT) photorheology experiments of thin films showed a rapid degelation in several seconds, whereas larger bulk samples could also be photocleaved. Furthermore, the gels could be reformed or healed by simple heating of the system and restoration of the metal-ligand crosslinks. The relatively simple dynamic system with a high sensitivity towards light in the visible and NIR region make them interesting positive photoresists for nano/micropatterning applications, as was demonstrated by writing, erasing, and rewriting of the gels by single- and multiphoton lithography.

Coumarin-Caged Polyphosphazenes with a Visible-Light Driven On-Demand Degradation.

Polymers that, upon photochemical activation with visible light, undergo rapid degradation to small molecules are described. Through functionalization of a polyphosphazene backbone with pendant coumarin groups sensitive to light, polymers which are stable in the dark could be prepared. Upon irradiation, cleavage of the coumarin moieties exposes carboxylic acid moieties along the polymer backbone. The subsequent macromolecular photoacid is found to catalyze the rapid hydrolytic degradation of the polyphosphazene backbone. Water-soluble and non-water-soluble polymers are reported, which due to their sensitivity toward light in the visible region could be significant as photocleavable materials in biological applications.

Synthesis of Trifluoroacetyl-Substituted Cyclopropanes Using Onium Ylides.

The use of carbonyl-stabilized ammonium- and sulfonium ylides allows for the synthesis of highly-functionalized trifluoroacetyl-substituted cyclopropanes. It turned out that the diastereoselectivities strongly depend on the nature of the chosen ylide and the employed base. The products could be obtained in good yields under operationally simple conditions.

Asymmetric Synthesis of 2,3-Dihydrobenzofurans by a [4+1] Annulation Between Ammonium Ylides and In Situ Generated o-Quinone Methides.

A highly enantio- and diastereoselective [4+1] annulation between in situ generated ammonium ylides and o-quinone methides for the synthesis of a variety of 2,3-dihydrobenzofurans has been developed. The key factors controlling the reactivity and stereoselectivity were systematically investigated by experimental and computational means and the energy profiles obtained provide a deeper insight into the mechanistic details of this reaction.

A Relativity Enhanced, Medium-Strong Au(I)···H-N Hydrogen Bond in a Protonated Phenylpyridine-Gold(I) Thiolate.

Gold is an electron-rich metal with a high electronegativity comparable to that of sulfur. Hence, hydrogen bonds of the Au(I)···H-E (E = electronegative element) type should be possible, but their existence is still under debate. Experimental results are scarce and often contradictory. As guidance for possible preparative work, we have theoretically investigated (ppyH)Au(SPh) (ppy = 2-phenylpyridine) bearing two monoanionic ligands which are not strongly electronegative at the same time to further increase the charge density on the gold(I) atom. The protonated pyridine nitrogen atom in ppy is geometrically ideally suited to place a proton in close proximity to the gold atom in a favorable geometry for a classical hydrogen bond arrangement. Indeed, the results of the calculations indicate that the hydrogen bonded conformation of (ppyH)Au(SPh) represents a minimum geometry with bond metrics in the expected range for medium-strong hydrogen bonds [r(N-H) = 1.043 Å, r(H···Au) = 2.060 Å, a(N-H···Au) = 141.4°]. The energy difference between the conformer containing the H···Au bond and another conformer without a hydrogen bond amounts to 7.8 kcal mol-1, which might serve as an estimate of the hydrogen bond strength. Spectroscopic properties were calculated, yielding further characteristics of such hydrogen bonded gold species.

Metallo-Supramolecular Gels that are Photocleavable with Visible and Near-Infrared Irradiation.

A photolabile ruthenium-based complex, [Ru(bpy)2 (4AMP)2 ](PF6 )2 , (4AMP=4-(aminomethyl)pyridine) is incorporated into polyurea organo- and hydrogels via the reactive amine moieties on the photocleavable 4AMP ligands. While showing long-term stability in the dark, cleavage of the pyridine-ruthenium bond upon irradiation with visible or near-infrared irradiation (in a two-photon process) leads to rapid de-gelation of the supramolecular gels, thus enabling spatiotemporal micropatterning by photomasking or pulsed NIR-laser irradiation.

N-Methylmelamines: Synthesis, Characterization, and Physical Properties.

N-Methylmelamines have recently gained importance as valuable compounds for manufacturing modified melamine formaldehyde resins and other polymer building blocks. A great advantage of these polymers is the reduction of the carcinogenic formaldehyde. Selecting the polymerization processes (e.g., substance polymerization, polymerization in solution) and controlling the polymerization reaction and properties of these novel materials requires knowledge of the properties of the individual melamine derivatives used as new building blocks. All possible permutations of N-methylmelamines were prepared, and reaction progress was monitored by GC/MS. 2,4,6-Tris(dimethylamino)-1,3,5-triazine was prepared to complete the series; this is, however, also a possible byproduct in various synthesis routes. The reaction conditions were optimized to obtain high yields of each derivative with the highest possible purity. The substances were characterized by NMR and IR spectroscopy, mass spectrometry, elemental analysis, and single-crystal X-ray diffraction. In addition, physical properties, such as solubility, melting points, and pKb values, were determined. The number of amino-, methylamino-, and dimethylamino groups has a significant effect on these properties. In summary, we found that by increasing the number of amino- and methylamino groups, solubility and pKb increase. With increasing number of amino groups, the compounds tend to form hydrogen bonds, and thus, the melting point shifts to higher temperature ranges where they start to decompose.

Highly efficient luminescence of Cu(I) compounds: thermally activated delayed fluorescence combined with short-lived phosphorescence.

Luminescent materials showing thermally activated delayed fluorescence (TADF) have gained high attractiveness as emitters in organic light emitting diodes (OLEDs) and other photonic applications. Nevertheless, even utilization of TADF can be further improved, introducing a novel concept. This is demonstrated by a new class of brightly luminescent low-cost Cu(I) compounds, for which the emission stems from both the lowest excited triplet T1 and singlet S1 state. At T = 300 K, these materials exhibit quantum yields of more than ΦPL = 90% at short emission decay times. About 80% of the emission intensity stems from the singlet due to TADF, but importantly, an additional 20% is contributed by the lower lying triplet state according to effective spin-orbit coupling (SOC). SOC induces also a relatively large zero-field splitting of the triplet being unusual for Cu(I) complexes. Thus, the overall emission decay time is distinctly reduced. Combined use of both decay paths opens novel photonic applications, in particular, for OLEDs.

Asymmetric syntheses of three-membered heterocycles using chiral amide-based ammonium ylides.

The use of carbonyl-stabilised ammonium ylides to access chiral glycidic amides and the corresponding aziridines has so far been limited to racemic trans-selective protocols. We herein report the development of an asymmetric approach to access such compounds with high levels of stereoselectivity using easily accessible chiral auxiliary-based ammonium ylides. The use of phenylglycinol as the chiral auxiliary was found to be superior to Evans or pseudoephedrine-based auxiliaries resulting in good to excellent stereoselectivities in both, epoxidation and aziridination reactions.

Hydrogen-bonded diketopyrrolopyrrole (DPP) pigments as organic semiconductors.

Diketopyrrolopyrroles (DPPs) have recently gained attention as building-blocks for organic semiconducting polymers and small molecules, however the semiconducting properties of their hydrogen-bonded (H-bonded) pigment forms have not been explored. Herein we report on the performance of three archetypical H-bonded DPP pigments, which show ambipolar carrier mobilities in the range 0.01-0.06 cm2/V s in organic field-effect transistors. Their semiconducting properties are correlated with crystal structure, where an H-bonded crystal lattice supports close and relatively cofacial π-π stacking. To better understand transport in these systems, density functional theory calculations were carried out, indicating theoretical maximum ambipolar mobility values of ∼0.3 cm2/V s. Based on these experimental and theoretical results, H-bonded DPPs represent a viable alternative to more established DPP-containing polymers and small molecules where H-bonding is blocked by N-alkylation.

Peptide coupling between amino acids and the carboxylic acid of a functionalized chlorido-gold(I)-phosphane.

We have developed a protocol for the direct coupling between methyl ester protected amino acids and the chlorido-gold(I)-phosphane (p-HOOC(C6H4)PPh2)AuCl. By applying the EDC·HCl/NHS strategy (EDC·HCl = N-ethyl-N'-(3-(dimethylamino)propyl)carbodiimide hydrochloride, NHS = N-hydroxysuccinimide), the methyl esters of l-phenylalanine, glycine, l-leucine, l-alanine, and l-methionine are coupled with the carboxylic acid of the gold complex in moderate to good yields (62-88%). All amino acid tagged gold complexes were characterized by (1)H and (13)C NMR spectroscopy and high-resolution mass spectrometry. As corroborated by measurement of the angle of optical rotation, no racemization occurred during the reaction. The molecular structure of the leucine derivative was determined by single-crystal X-ray diffraction. In the course of developing an efficient coupling protocol, the acyl chlorides (p-Cl(O)C(C6H4)PPh2)AuX (X = Cl, Br) were also prepared and characterized.

Synthesis and characterization of redox-active charge-transfer complexes with 2,3,5,6-tetracyanopyridine (TCNPy) for the photogeneration of pyridinium radicals.

The heteroaromatic polynitrile compound tetracyanopyridine (TCNPy) is introduced as a new electron acceptor for the formation of deeply colored charge-transfer complexes. In MeCN, TCNPy is characterized by a quasireversible one-electron-reduction process at -0.51 V (versus SCE). The tetracyanopyridine radical anion undergoes a secondary chemical reaction, which is assigned to a protonation step. TCNPy has been demonstrated to generate 1:1 complexes with various electron donors, including tetrathiafulvalene (TTF) and dihydroxybenzene derivatives, such as p-hydroquinone and catechol. Visible- or NIR-light-induced excitation of the intense charge-transfer bands of these compounds leads to a direct optical electron-transfer process for the formation of the corresponding radical-ion pairs. The presence of available electron donors that contain protic groups in close proximity to the TCNPy acceptor site opens up a new strategy for the photocontrolled generation of pyridinium radicals in a stepwise proton-coupled electron-transfer (PCET) sequence.

Synthesis, structure, and characterization of dinuclear copper(I) halide complexes with P

A series of highly luminescent dinuclear copper(I) complexes has been synthesized in good yields using a modular ligand system of easily accessible diphenylphosphinopyridine-type P^N ligands. Characterization of these complexes via X-ray crystallographic studies and elemental analysis revealed a dinuclear complex structure with a butterfly-shaped metal-halide core. The complexes feature emission covering the visible spectrum from blue to red together with high quantum yields up to 96%. Density functional theory calculations show that the HOMO consists mainly of orbitals of both the metal core and the bridging halides, while the LUMO resides dominantly on the heterocyclic part of the P^N ligands. Therefore, modification of the heterocyclic moiety of the bridging ligand allows for systematic tuning of the luminescence wavelength. By increasing the aromatic system of the N-heterocycle or through functionalization of the pyridyl moiety, complexes with emission maxima from 481 to 713 nm are obtained. For a representative compound, it is shown that the ambient-temperature emission can be assigned as a thermally activated delayed fluorescence, featuring an attractively short emission decay time of only 6.5 µs at ϕPL = 0.8. It is proposed to apply these compounds for singlet harvesting in OLEDs.

Synthesis and characterisation of cobalt, nickel and copper complexes with tripodal 4N ligands as novel catalysts for the homogeneous partial oxidation of alkanes.

Four new compounds of the general formula [M(L)(CH3COO)][PF6], where L is a tetradentate tripodal ligand such as tris[2-(dimethylamino)ethyl]amine (L1) or (2-aminoethyl)bis(2-pyridylmethyl)amine (L2) and M is Co(II), Ni(II) or Cu(II), have been prepared employing a simple two-step synthesis. The compounds have been characterised by elemental analysis, mass spectroscopy, IR spectroscopy and X-ray diffraction. The catalytic properties of the derivatives containing the aliphatic ligand L1 have been investigated in particular toward the oxidation of cyclohexane and adamantane in the presence of the sacrificial oxidant m-CPBA (meta-chloroperbenzoic acid). Good TONs and selectivity have been determined for the cobalt and nickel compounds.

Aurophilic Molecules on Surfaces. Part I. (NapNC)AuCl on Au(110).

Aurophilicity is a well-known phenomenon in structural gold chemistry and is found in many crystals of Au(I) complexes. However, these attractive dispersion forces between and within complexes containing Au(I) moieties have not been well studied in ultrathin films. In this paper, we elucidate the interaction of chlorido(2-naphthyl isonitrile)gold(I) on and with Au(110) surfaces. Already during physical vapor deposition, the condensation of ultrathin films is monitored by photoelectron emission microscopy (PEEM) and by incremental and spectrally resolved changes in the optical reflectance (DDRS). Additional structural data obtained by STM and LEED reveal that the "crossed swords" packing motif known from the bulk is also present in thin films. The molecular arrangement changes several times during thin-film deposition.