Combined spectroscopic studies on post-functionalized Au cluster as an ATR-FTIR sensor for cations.

Recently, significant research activity has been devoted to thiolate-protected gold clusters due to their attractive optical and electronic properties. These properties as well as solubility and stability can be controlled by post-synthetic modification strategies. Herein, the ligand exchange reaction between Au(2-PET) cluster (where 2-PET is 2-phenylethanethiol) and di-thiolated crown ether (-CE) ligands bearing two chromophores was studied.

Unconventional Approaches in Coordination Chemistry and Organometallic Reactivity.

This contribution highlights a number of approaches developed by coordination and organometallic chemists that go beyond mainstream inorganic reactivity. A few of these strategies have been known for decades and are fundamental tools in synthesis and catalysis, while others are more recent and still belong to a niche. Through selected examples, we show herein how transmetalation, metal exchange, metal cooperativity, and catalytic transformation of metal complexes provide unique new opportunities to expand the reactivity arsenal of inorganic systems for synthetic and technological applications.

The Zn(II)-1,4,7-Trimethyl-1,4,7-Triazacyclononane Complex: A Monometallic Catalyst Active in Two Protonation States.

In this paper, the unusual reactivity of the complex Zn(II)-1,4,7-trimethyl-1, 4,7-triazacyclononane () in the transesterification of the RNA-model substrate, (), is reported. The dependence of the reactivity (k) with pH does not follow the characteristic bell-shape profile typical of complexes with penta-coordinated metal centers. By the contrary, two reactive species, featuring different deprotonation states, are present, with the tri-aqua complex being more reactive than the mono-hydroxy-diaqua one.

Metal Complexes of Oxadiazole Ligands: An Overview.

Oxadizoles are heterocyclic ring systems that find application in different scientific disciplines, from medicinal chemistry to optoelectronics. Coordination with metals (especially the transition ones) proved to enhance the intrinsic characteristics of these organic ligands and many metal complexes of oxadiazoles showed attractive characteristics for different research fields. In this review, we provide a general overview on different metal complexes and polymers containing oxadiazole moieties, reporting the principal synthetic approaches adopted for their preparation and showing the variety of applications they found in the last 40 years.

Dynamic Origin of Chirality Transfer between Chiral Surface and Achiral Ligand in Au Clusters.

The transfer of chirality between nanomolecules is at the core of several applications in chiral technology such as sensing and catalysis. However, the origin of this phenomenon and how exactly nanoscale objects transfer chirality to molecules in their vicinity remain largely obscure. Here, we show that the transfer of chirality for the intrinsically chiral gold cluster Au(SR) is site dependent; that is, it differs depending on the ligand-binding sites.

Ligand Migration from Cluster to Support: A Crucial Factor for Catalysis by Thiolate-protected Gold Clusters.

Thiolate protected metal clusters are valuable precursors for the design of tailored nanosized catalysts. Their performance can be tuned precisely at atomic level, e. g.

Covalently bonded multimers of Au(SBut) as a conjugated system.

Aromatic dithiol linkers were used to prepare aggregates of Au25(SR)18 clusters (SR: thiolate) via ligand exchange reactions. Fractions of different aggregate sizes were separated by size exclusion chromatography (SEC). The aggregates were characterized by UV-vis absorption spectroscopy, matrix assisted laser desorption ionization (MALDI) mass spectrometry, nuclear magnetic resonance (NMR) spectroscopy (including diffusion-ordered spectroscopy, DOSY) and small angle X-ray scattering (SAXS).

On the mechanism of rapid metal exchange between thiolate-protected gold and gold/silver clusters: a time-resolved in situ XAFS study.

The fast metal exchange reaction between Au and AgAu nanoclusters in solution at -20 °C has been studied by in situ X-ray absorption spectroscopy (time resolved quick XAFS) in transmission mode. A cell was designed for this purpose consisting of a cooling system, remote injection and mixing devices. The capability of the set-up is demonstrated for second and minute time scale measurements of the metal exchange reaction upon mixing Au/toluene and AgAu/toluene solutions at both Ag K-edge and Au L-edge.

Dynamic Nature of Thiolate Monolayer in Au(SR) Nanoclusters.

Thiolate monolayer, protecting a gold nanocluster, is responsible for its chemical behavior and interaction with the environment. Understanding the parameters that influence the stability and reactivity of the monolayer will enable its precise and controlled functionalization. Here we present a protocol for the investigation of the monolayer reactivity in Au(SR) based on MALDI mass spectrometry and NMR spectroscopy.

Silver migration between Au38(SC2H4Ph)24 and doped AgxAu38-x(SC2H4Ph)24 nanoclusters.

A fast redistribution of metal atoms occurs upon mixing the AgxAu38-x and Au38 nanoclusters in solution, as observed by mass spectrometry. Physical separation of AgxAu38-x and Au38 species by a dialysis membrane prohibits the metal migration, which suggests that collisions between the reacting clusters are at the origin of the observation.

Turning Supramolecular Receptors into Chemosensors by Nanoparticle-Assisted "NMR Chemosensing".

By exploiting a magnetization transfer between monolayer-protected nanoparticles and interacting analytes, the NMR chemosensing protocol provides a general approach to convert supramolecular receptors into chemosensors via their conjugation with nanoparticles. In this context, the nanoparticles provide the supramolecular receptor not only with the "bulkiness" necessary for the NMR chemosensing approach but also with a different selectivity as compared to the parent receptor. We here demonstrate that gold nanoparticles of 1.

Spectroscopic properties of Zn(salphenazine) complexes and their application in small molecule organic solar cells.

A new family of salphen based complexes, viz. Zn(salphenazine)s, has been prepared and is characterized by a larger π-surface compared to previously reported Zn(salphen) complexes. The spectroscopic properties of these Zn(salphenazine)s have been studied in detail using UV-Vis and fluorescence spectroscopy, and further investigated by computational methods.

Supramolecular bulky phosphines comprising 1,3,5-triaza-7-phosphaadamantane and Zn(salphen)s: structural features and application in hydrosilylation catalysis.

The use of the commercially available, bifunctional phosphine 1,3,5-triaza-7-phosphaadamantane (abbreviated as PN3) in conjunction with a series of Zn(salphen) complexes leads to sterically encumbered phosphine ligands as a result of (reversible) coordinative Zn-N interactions. The solid state and solution phase behaviour of these supramolecular ligand systems have been investigated in detail and revealed their stoichiometries in the solid state observed by X-ray crystallography, and those determined in solution by NMR and UV-Vis spectroscopy. Also, upon application of these supramolecular bulky phosphines in hydrosilylation catalysis employing 1-hexene as a substrate, the catalysis data infer the presence of an active Rh species with two coordinated, bulky PN3/Zn(salphen) assembly units having a maximum of three Zn(salphen)s associated per PN3 scaffold, with an excess of bulky phosphines hardly affecting the overall activity.

A DFT study on the mechanism of the cycloaddition reaction of CO2 to epoxides catalyzed by Zn(salphen) complexes.

The reaction mechanism for the Zn(salphen)/NBu4X (X = Br, I) mediated cycloaddition of CO2 to a series of epoxides, affording five-membered cyclic carbonate products has been investigated in detail by using DFT methods. The ring-opening step of the process was examined and the preference for opening at the methylene (Cβ) or methine carbon (Cα) was established. Furthermore, calculations were performed to clarify the reasons for the lethargic behavior of internal epoxides in the presence of the binary catalyst.

Merging catalysis and supramolecular aggregation features of triptycene based Zn(salphen)s.

A series of trinuclear, triptycene-based metallosalphen complexes (M = Zn, Ni) have been prepared incorporating various peripheral substituents. The introduction of Zn metal centres into these triptycene based salphen ligands gives rise to cross-linking between different triptycene molecules through μ-phenoxo bridges between the Zn metal centres, and variation in the peripheral groups allows the control of the self-assembling properties as shown by UV-Vis titration data. The strong association of these trinuclear Zn3 complexes under relatively apolar conditions has been exploited to recover the complex after its application as a catalyst in the cycloaddition of carbon dioxide to 1,2-epoxyhexane.

Versatile switching in substrate topicity: supramolecular chirality induction in di- and trinuclear host complexes.

Supramolecular chirality effects have been achieved both for ditopic and monotopic substrates by using a programmable bis-salphen scaffold that incorporates either two or three Zn nuclei. The dinuclear host shows preferential chirogenesis in the presence of ditopic systems, whereas effective chirality transfer to the trinuclear complex is realized through monotopic binding. The mode of binding in the trinuclear host has been investigated through X-ray crystallography, CD measurements, UV/Vis spectroscopy, and DFT analysis.

Extremely strong self-assembly of a bimetallic salen complex visualized at the single-molecule level.

A bis-Zn(salphen) structure shows extremely strong self-assembly both in solution as well as at the solid-liquid interface as evidenced by scanning tunneling microscopy, competitive UV-vis and fluorescence titrations, dynamic light scattering, and transmission electron microscopy. Density functional theory analysis on the Zn(2) complex rationalizes the very high stability of the self-assembled structures provoked by unusual oligomeric (Zn-O)(n) coordination motifs within the assembly. This coordination mode is strikingly different when compared with mononuclear Zn(salphen) analogues that form dimeric structures having a typical Zn(2)O(2) central unit.

Recent advances with π-conjugated salen systems.

Schiff base ligands have long been successfully employed as ligands in combination with various metals to give catalysts capable of realizing a variety of synthetic transformations. One of the most widely used Schiff base ligands, the "salen" ligand, has been extensively researched. Recently, there has been increased interest in π-conjugated salen systems, known as "salphen" ligands, as a result of the differences in reactivity of the complexes in catalytic applications compared with the salen analogues.

A short desymmetrization protocol for the coordination environment in bis-salphen scaffolds.

A remarkable short preparation of desymmetrized bis-salphen scaffolds is presented. The protocol consists of an hydroxide-mediated hydrolysis of Lewis acidic bis-Zn(salphen) complexes yielding C(s)-symmetric diimine/amine salts that can be selectively transformed into bis-salphens with dissymmetric substitution patterns within each salphen unit under mild conditions. These isolated nonsymmetrical bis-salphen derivatives do not show signs of imine scrambling or decomposition due to a metal template effect.

Cooperative self-assembly of a macrocyclic Schiff base complex.

A metal template approach affords in high yield a tetra-Zn(salphen) macrocycle (3) which shows strong and cooperative self-assembly mediated by the formation of Zn(salphen) dimer units held together via μ(2)-phenoxo interactions. A cooperative binding mode for the tetranuclear Zn(4) macrocycle 3 is supported by comparison of UV-vis and fluorescence titration data recorded for 3 when compared with respective mononuclear and dinuclear Zn(salphen) model compounds. UV-vis dilution experiments carried out for Zn(4) macrocycle 3 and its Pd(4) analogue 4, as well as comparative TEM studies involving the same tetranuclear macrocycles further support the strong assembly behavior of 3.

Ligand-selective photodissociation from [Ru(bpy)(4AP)4]2+: a spectroscopic and computational study.

The new complex [Ru(bpy)(4AP)(4)](2+) (1), where bpy = 2,2'-bipyridine and 4AP = 4-aminopyridine, undergoes selective photodissociation of two 4APs upon light excitation of the metal-ligand-to-ligand charge-transfer (MLLCT) band at 510 nm. The photoproducts of the reaction are mer-[Ru(bpy)(4AP)(3)(H(2)O)](2+) (2a) and trans-(4AP)[Ru(bpy)(4AP)(2)(H(2)O)(2)](2+) (3a). Photodissociation occurs in two consecutive steps with quantum yields of phi(1) = (6.

Mechanism of ligand photodissociation in photoactivable [Ru(bpy)2L2]2+ complexes: a density functional theory study.

A series of four photodissociable Ru polypyridyl complexes of general formula [Ru(bpy)2L2](2+), where bpy = 2,2'-bipyridine and L = 4-aminopyridine (1), pyridine (2), butylamine (3), and gamma-aminobutyric acid (4), was studied by density functional theory (DFT) and time-dependent density functional theory (TDDFT). DFT calculations (B3LYP/LanL2DZ) were able to predict and elucidate singlet and triplet excited-state properties of 1-4 and describe the photodissociation mechanism of one monodentate ligand. All derivatives display a Ru --> bpy metal-to-ligand charge transfer (MLCT) absorption band in the visible spectrum and a corresponding emitting triplet (3)MLCT state (Ru --> bpy).