Electropolymerizable IrIII Complexes with β‐Ketoiminate Ancillary Ligands

A series of electropolymerizable cyclometallated Ir^III complexes were synthesized and their electrochemical and photophysical properties studied. The triphenylamine electropolymerizable fragment was introduced by using triphenylamine‐2‐phenylpyridine and, respectively, triphenylamine‐benzothiazole as cyclometalated ligands. The coordination sphere was completed by two differently substituted β‐ketoiminate ligands deriving from the condensation of acetylacetone or hexafluoroacetylacetone with para‐bromoaniline. The influence of the ‐CH₃/‐CF₃ substitution to the electrochemical and photophysical properties was investigated. Both complexes with CH₃ substituted β‐ketoiminate were emissive in solution and in solid state. Highly stable films were electrodeposited onto ITO coated glass substrates. Their emission was quenched by electron trapping within the polymeric network as proven by electrochemical studies. The ‐CF₃ substitution of the β‐ketoiminate leads instead to the quenching of the emission and inhibits electropolymerization.     

Cyclometalated Mono‐ and Dinuclear IrIII Complexes with “Click”‐Derived Triazoles and Mesoionic Carbenes

Orthometalation at Ir^III centers is usually facile, and such orthometalated complexes often display intriguing electronic and catalytic properties. By using a central phenyl ring as C?H activation sites, we present here mono‐ and dinuclear Ir^III complexes with “click”‐derived 1,2,3‐triazole and 1,2,3‐triazol‐5‐ylidene ligands, in which the wingtip phenyl groups in the aforementioned ligands are additionally orthometalated and bind as carbanionic donors to the Ir^III centers. Structural characterization of the complexes reveal a piano stool‐type of coordination around the metal centers with the “click”‐derived ligands bound either with C^N or C^C donor sets to the Ir^III centers. Furthermore, whereas bond localization is observed within the 1,2,3‐triazole ligands, a more delocalized situation is found in their 1,2,3‐triazol‐5‐ylidene counterparts. All complexes were subjected to catalytic tests for the transfer hydrogenation of benzaldehyde and acetophenone. The dinuclear complexes turned out to be more active than their mononuclear counterparts. We present here the first examples of stable, isomer‐pure, dinuclear cyclometalated Ir^III complexes with poly‐mesoionic‐carbene ligands.     

2‐(1 H‐1,2,3‐Triazol‐4‐yl)‐Pyridine Ligands as Alternatives to 2,2′‐Bipyridines in Ruthenium(II) Complexes

The synthesis of a variety of 2‐(1H‐1,2,3‐triazol‐4‐yl)‐pyridines by click chemistry is demonstrated to provide straightforward access to mono‐functionalized ligands. The ring‐opening polymerization of ε‐caprolactone initiated by such a mono‐functionalized ligand highlights the synthetic potential of this class of bidentate ligands with respect to polymer chemistry or the attachment onto surfaces and nanoparticles. The coordination to Ru^II ions results in homoleptic and heteroleptic complexes with the resultant photophysical and electrochemical properties strongly dependent on the number of these ligands attached to the Ru^II core.     

Heptyl α‐D‐Mannosides Grafted on a β‐Cyclodextrin Core To Interfere with Escherichia coli Adhesion: An In Vivo Multivalent Effect

n‐Heptyl α‐D ‐mannoside (HM) has previously been identified as a nanomolar FimH antagonist able to prevent Escherichia coli adhesion. We have designed mono‐ and heptavalent glycoconjugates in which HM is tethered to β‐cyclodextrin (β‐CD) through short and long spacers. One‐pot click or co‐clicking procedures were developed to directly obtain the glycoconjugates from unprotected HM and β‐CD precursors. These FimH antagonists were examined biophysically and in vivo. Reverse titrations by isothermal calorimetry led to trapping of the short‐tethered heptavalent β‐CD in a complex with three FimH lectins. Combined dynamic light scattering and small‐angle X‐ray solution scattering data allowed the construction of a model of the FimH trimer. The heptavalent β‐CDs were shown to capture and aggregate living bacteria in solution and are therefore also able to aggregate FimH when attached to different bacteria pili. The first in vivo evaluation of multivalent FimH inhibitors has been performed. The heptavalent β‐CDs proved to be much more effective anti‐adhesive agents than monovalent references with doses of around 2 μg instilled in the mouse bladder leading to a significantly decreased E. coli load. Intravenously injected radiolabeled glycoconjugates can rapidly reach the mouse bladder and >2 μg concentrations can easily be retained over 24 h to prevent fluxing bacteria from rebinding.     

RuII,OsII, and IrIII Complexes with Chelating Pyridyl–Mesoionic Carbene Ligands: Structural Characterization and Applications in Transfer Hydrogenation Catalysis

Chelating ligands with one pyridine donor and one mesoionic carbene donor are fast establishing themselves as privileged ligands in homogeneous catalysis. The synthesis of several new Ir^III–Cp*‐ and Os^II–Cym complexes (Cp*=pentamethylcyclopentadienyl, Cym=p‐cymene=4‐isopropyl‐toluene) derived from chelating pyridyltriazolylidenes where the additional pyridine donor was incorporated via the azide part of the triazole is presented. Furthermore, different 4‐substituted phenylacetylene building blocks have been used to introduce electronic fine‐tuning in the ligands. The ligands thus can be generally described as 4‐(4‐R‐phenyl)‐3‐methyl‐1‐(pyridin‐2‐yl)‐1H‐1,2,3‐triazol‐5‐ylidene (with R being H (L¹), Me (L²), OMe (L³), CN (L⁴), CF₃ (L⁵), Br (L⁶) or NO₂ (L⁷)). The corresponding complexes (Ir‐ 1 to Ir‐ 7 and Os‐ 1 to Os‐ 7 ) were characterized by standard spectroscopic methods, and the expected three‐legged, piano‐stool type coordination was unambiguously confirmed by X‐ray diffraction analysis of selected compounds. Together with Ru^II analogues previously reported by us, a total of 21 complexes were tested as (pre)catalysts for the transfer hydrogenation of carbonyl groups, showing a remarkable reactivity even at very low catalyst loadings. The electronic effects of the ligands as well as different substrates were investigated. Some mechanistic elucidations are also presented.     

β‐Cyclodextrin Pseudopolyrotaxanes with π‐Conjugated Polymer Axles

Summary: β‐Cyclodextrin (β‐CD) pseudopolyrotaxanes containing poly(thiophene‐2,5‐diyl), PTh , or poly(3‐methylthiophene‐2,5‐diyl)s, P3MeTh s, as an axle were prepared. Structures of the pseudopolyrotaxanes and their inclusion behavior with β‐CD were investigated. The UV‐vis measurements revealed that inclusion of P3MeTh s by β‐CD depended on the flexibility of the main chain and their molecular weight.

Formation of the inclusion complex of β‐CD and PTh .     

RuII and IrIII Complexes Containing ADA and DAD Triple Hydrogen Bonding Motifs: Potential Tectons for the Assembly of Functional Materials

The synthesis and characterisation of a series of [Ru^II(bpy)₂L] and [Ir(ppy)₂L] complexes containing ligands L with the potential to engage in triple hydrogen bonding interactions is described. L1 and L2 comprise pyridyl triazole chelating units with pendant diaminotriazine units, capable of donor‐acceptor‐donor (DAD) hydrogen bonding, while L3 and L4 contain ADA hydrogen bonding units proximal to N^N and N^O cleating sites, respectively. X‐ray crystallography shows the L1 and L2 containing Ru^II complexes to assemble via hydrogen bonding dimers, while [Ru^II(bpy)₂L 4 ] assembles via extended hydrogen bonding motifs to form one dimensional chains. By contrast, the expected hydrogen bonding patterns are not observed for the Ru^II and Ir^III complexes of L3 . Spectroscopic studies show that the absorption spectra of the complexes result from combinations of MLCT and LLCT transitions. The L1 and L2 complexes of Ir^III and Ru^II complexes are emissive in the solid state and it seems likely that hydrogen bonding to complementary species may facilitate tuning of their ³ILCT emission. Low frequency Raman spectra provide further evidence for ordered interactions in the solid state for the L4 complexes, consistent with the results from X‐ray crystallography.     

Stepwise Strategy to Cyclometallated PtII Complexes with N‐Heterocyclic Carbene Ligands: A Luminescence Study on New β‐Diketonate Complexes

The imidazolium salt 3‐methyl‐1‐(naphthalen‐2‐yl)‐1H‐imidazolium iodide ( 2 ) has been treated with silver(I) oxide and [{Pt(μ‐Cl)(η³‐2‐Me‐C₃H₄)}₂] (η³‐2‐Me‐C₃H₄=η³‐2‐methylallyl) to give the intermediate N‐heterocyclic carbene complex [PtCl(η³‐2‐Me‐C₃H₄)(H$\widehat{CC}$ *‐κC*)] ( 3 ) (H$\widehat{CC}$ *‐κC*=3‐methyl‐1‐(naphthalen‐2‐yl)‐1H‐imidazol‐2‐ylidene). Compound 3 undergoes regiospecific cyclometallation at the naphthyl ring of the NHC ligand to give the five‐membered platinacycle compound [{Pt(μ‐Cl)($\widehat{CC}$ *)}₂] ( 4 ). Chlorine abstraction from 4 with β‐diketonate Tl derivatives rendered the corresponding neutral compounds [Pt($\widehat{CC}$ *)(L‐O,O′)] {L=acac (HL=acetylacetone) 5 , phacac (HL=1,3‐diphenyl‐1,3‐propanedione) 6 , hfacac (HL=hexafluoroacetylacetone) 7 }. All of the compounds ( 3 – 7 ) were fully characterized by standard spectroscopic and analytical methods. X‐ray diffraction studies were performed on 5 – 7 , revealing short Pt?Pt and π–π interactions in the solid‐state structure. The influence of the R‐substituents of the β‐diketonate ligand on the photophysical properties and the use of the most efficient emitter, 5 , as phosphor converter has also been studied.     

Protein Labelling with Versatile Phosphorescent Metal Complexes for Live Cell Luminescence Imaging

To take advantage of the luminescent properties of d⁶ transition metal complexes to label proteins, versatile bifunctional ligands were prepared. Ligands that contain a 1,2,3‐triazole heterocycle were synthesised using Cu^I catalysed azide–alkyne cycloaddition “click” chemistry and were used to form phosphorescent Ir^III and Ru^II complexes. Their emission properties were readily tuned, by changing either the metal ion or the co‐ligands. The complexes were tethered to the metalloprotein transferrin using several conjugation strategies. The Ir^III/Ru^II–protein conjugates could be visualised in cancer cells using live cell imaging for extended periods without significant photobleaching. These versatile phosphorescent protein‐labelling agents could be widely applied to other proteins and biomolecules and are useful alternatives to conventional organic fluorophores for several applications.     

Host‐Assisted Guest Self‐Assembly: Enhancement of the Dimerization of Pyronines Y and B by γ‐Cyclodextrin

Buckle up! The dimerization of small fluorescent guests is strongly enhanced in presence of a cyclodextrin host. The host cavity acts like a belt to assist the self‐assembly of guests (see picture). Small variations in the guest structure have significant influence on the stability and geometry of the aggregates.

     

Design and Synthesis of a γ1β8‐Cyclodextrin Oligomer: A New Platform with Potential Application as a Dendrimeric Multicarrier

We report the synthesis and characterization of a water‐soluble, star‐shaped macromolecular platform consisting of eight β‐cyclodextrin (β‐CD) units anchored to the narrower rim of a γ‐CD core through bis(triazolyl)alkyl spacers. The efficient synthetic protocol is based on the microwave (MW)‐promoted Cu‐catalyzed 1,3‐dipolar cycloaddition of CD monoazides to CD monoacetylenes. The ligand‐hosting capability of the construct has been assessed by relaxometric titration and nuclear magnetic relaxation dispersion (NMRD) profiling, which showed it to be good, and this was supported by molecular dynamics simulations. To demonstrate the feasibility of obtaining supramolecular structures with high hosting ability, we designed a dimeric platform, formed by joining two nonamers through the γ‐CD cores through a bis(lithocholic acid) linker. With a view to the potential biological applications, cytotoxicity and extent of binding to human serum albumin were assessed. The properties of this dendrimeric multicarrier make it suitable for pharmaceutical and diagnostic purposes, ranging from targeted drug delivery to molecular imaging.     

Ruthenium Complexes of Tripodal Ligands with Pyridine and Triazole Arms: Subtle Tuning of Thermal,Electrochemical, and Photochemical Reactivity

Electrochemical and photochemical bond‐activation steps are important for a variety of chemical transformations. We present here four new complexes, [Ru(Lⁿ)(dmso)(Cl)]PF₆ ( 1 – 4 ), where Lⁿ is a tripodal amine ligand with 4?n pyridylmethyl arms and n?1 triazolylmethyl arms. Structural comparisons show that the triazoles bind closer to the Ru center than the pyridines. For L², two isomers (with respect to the position of the triazole arm, equatorial or axial), trans‐ 2 _sym and trans‐ 2 _un, could be separated and compared. The increase in the number of the triazole arms in the ligand has almost no effect on the Ru^II/Ru^III oxidation potentials, but it increases the stability of the Ru?S_dmso bond. Hence, the oxidation waves become more reversible from trans‐ 1 to trans‐ 4 , and whereas the dmso ligand readily dissociates from trans‐ 1 upon heating or irradiation with UV light, the Ru?S bond of trans‐ 4 remains perfectly stable under the same conditions. The strength of the Ru?S bond is not only influenced by the number of triazole arms but also by their position, as evidenced by the difference in redox behavior and reactivity of the two isomers, trans‐ 2 _sym and trans‐ 2 _un. A mechanistic picture for the electrochemical, thermal, and photochemical bond activation is discussed with data from NMR spectroscopy, cyclic voltammetry, and spectroelectrochemistry.     

RuII Multinuclear Metallosupramolecular Rack‐Type Architectures of Polytopic Hydrazone‐Based Ligands: Synthesis,Structural Features,Absorption Spectra,Redox Behavior,and Near‐Infrared Luminescence

A novel class of polytopic hydrazone‐based ligands was synthesized. They gave heteroleptic Ru^II polynuclear rack‐like complexes of formula [Ru_nterpy_n(bridging molecular strand)]²ⁿ⁺ (terpy=2,2′:6′,2′′‐terpyridine). The new rack‐like systems can be viewed as being made of two identical or roughly identical peripheral subunits separated by several similar metal‐containing spacer subunits. The presence of pyrazine or pyrimidine units within the molecular multitopic strands introduces additional chemical diversity: whereas a pyrimidine unit leads to appended orthogonal subunits that are on the same side with regard to the main molecular strand, a pyrazine unit leads to orthogonal subunits that lie on different sides. Mixing pyrazine and pyrimidine units within the same (bridging) molecular strand also allows peculiar and topographically controlled geometries to be obtained. Redox studies provided evidence that each species undergoes reversible redox processes at mild potentials, which can be assigned to specific subunits of the multicomponent arrays. Non‐negligible electronic coupling takes place among the various subunits, and some electron delocalization extending over the overall bridging molecular strand takes place. In particular, oxidation data suggest that the systems can behave as p‐type “molecular wires” and reduction data indicate that n‐type electron conduction can occur within the multimetallic framework. All the multinuclear racks exhibit ³MLCT emission, both at 77 K in rigid matrix and at 298 K in fluid solution, which takes place in the near‐infrared region (emission maxima in the 1000–1100 nm region), and is quite structured. Rigidity of the molecular structures and delocalization within the large bridging ligands are proposed to contribute to the occurrence of the rather uncommon MLCT infrared emission, which is potentially interesting for optical communication devices.     

Iron and Nickel Complexes Containing β‐Diketiminato Ligands with Thioether Tethers

A novel β‐diketiminato ligand precursor, LH ( II ), containing thioether tethers was synthesized by the reaction of acetylacetone and 2‐methylthioaniline. II was deprotonated and used in the synthesis of two iron(II) complexes, [LFeCl] ( 1 ), and [LFeOTf] ( 2 ), and one nickel(II) complex, [LNiBr] ( 3 ). All three compounds were characterized by means of single crystal X‐ray diffraction and their structures are discussed.     

Photophysical Properties of Heteroleptic Iridium Complexes Containing Carbazole‐Functionalized β‐Diketonates

Twelve iridium complexes with general formula of Ir(C^N)₂(LX) [C^N represents the cyclometalated ligand, i.e. 2‐(2,4‐difluorophenyl) pyridine (dfppy), 2‐phenylpyridine (ppy), dibenzo{f, h}quinoxaline (DBQ); LX stands for β‐diketonate, i.e. acetyl acetonate (acac), 1‐(carbazol‐9‐yl)‐5,5‐dimethylhexane‐2,4‐diketonate (CBDK), 1‐(carbazol‐9‐yl)‐5,5,6,6,7,7,7‐heptafluoroheptane‐2,4‐diketonate (CHFDK), 1‐(N‐ethyl‐carbazol‐3‐yl)‐4,4,5,5,6,6,6‐heptafluorohexane‐1,3‐diketonate (ECHFDK)] are synthesized, characterized and their photophysical properties are systemically studied. In addition, crystals of Ir(DBQ)₂(CHFDK) and Ir(DBQ)₂(acac) are obtained and characterized by single crystal X‐ray diffraction. The choice of these iridium complexes provides an opportunity for tracing the effect of the triplet energy level of ancillary ligands on the photophysical and electrochemical behaviors. Data show that if the triplet energy level of the β‐diketonate is higher than that of the Ir(C^N)₂ fragment and there is no superposition on the state density map, strong ³LC or ³MLCT‐based phosphorescence can be obtained. Alternatively, if the state density map of the two parts are in superposition, the ³LC or ³MLCT‐based transition will be quenched at room temperature. Density functional theory calculations show that these complexes can be divided into two categories. The lowest excited state is mainly determined by C^N but not β‐diketonate when the difference between the triplet energy levels of the two parts is large. However, when this difference is very small, the lowest excited state will be determined by both sides. This provides a satisfactory explanation for the experimental observations.     

Easy Separation of Δ and Λ Isomers of Highly Luminescent [IrIII]‐Cyclometalated Complexes Based on Chiral Phenol‐Oxazoline Ancillary Ligands

A new class of neutral cyclometalated iridium(III) complexes with enantiomerically pure C₁‐symmetric phenol‐oxazolines ( 3 a,b ) have been synthetized in high yields and fully characterized. Resolution of the corresponding Δ_R and Λ_R or Δ_S and Λ_S isomers was easily achieved by conventional flash chromatography. The corresponding Δ and Λ helicities have been confirmed by CD spectroscopy and X‐ray crystallography. Regarding the absorption and luminescence properties with unpolarized light, no significant difference between Δ and Λ isomers has been observed. A strong blue luminescence is observed for deaerated solutions of complexes 5 a and 5 b in CH₃CN.     

Optimal Configurations of “Capped” β‐Cyclodextrin Dimers in Water Maximise Hydrophobic Association

Circular dichroism analysis and proton NMR experiments revealed that solutions of 3‐O‐(2‐methylnaphthyl)‐β‐cyclodextrin form different dimer configurations. The exact nature of the dimer configurations were postulated to be of three types in which these capped cyclodextrins (CDs) are orientated in head‐to‐head and head‐to‐tail arrangements. Here we show from detailed computer simulations and free‐energy calculations on the configurations that the head‐to‐head configuration in which the naphthyl groups are mutually inserted into each other’s CD cavities is the most favoured configuration. This configuration optimises the hydrophobic association of the naphthyl aromatic groups and the ring cavities as well as forming the most inter‐CD hydrogen bonds of the three configurations.