Tin-Chelated Trisphosphineoxide Scorpionate Rare-Earth Porphyrinate Complexes: Synthesis and Photophysical Properties.

A series of seven-coordinated monoporphyrinate rare-earth(III) complexes featuring a novel tripodal tin-chelated trisphosphineoxide scorpionate ligand with the general formula [(TPP)Ln(PPhO)Sn] (Ln = Y, La, Dy, Er, Ho, Yb; TPP = 5,10,15,20-tetraphenylporphyrinate) were synthesized by reactions of the potassium tripodal scorpionate ligand [Sn(PPhO)K] with porphyrinate rare-earth metal chlorides [(TPP)LnCl(dme)] (Ln = Y, Dy, Er, Ho, Yb) or porphyrinate lanthanum borohydride [(TPP)LaBH(thf)]. The complexes were characterized by single-crystal X-ray diffraction, NMR spectroscopy, and ion mobility mass spectrometry. All complexes emit weak red TPP-based fluorescence, accompanied by near-infrared emission of Er, Ho (rather weak), and Yb (relatively intense with a quantum yield of 1% in dichloromethane solution) of the corresponding complexes.

Chirality Detection in Scanning Tunneling Microscopy Data Using Artificial Intelligence.

Enantiospecific effects play an uprising role in chemistry and technical applications. Chiral molecular networks formed by self-assembly processes at surfaces can be imaged by scanning probe microscopy (SPM). Low contrast and high noise in the topography map often interfere with the automatic image analysis using classical methods.

Controlling Nanoparticle Distance by On-Surface DNA-Origami Folding.

DNA origami is a flexible platform for the precise organization of nano-objects, enabling numerous applications from biomedicine to nano-photonics. Its huge potential stems from its high flexibility that allows customized structures to meet specific requirements. The ability to generate diverse final structures from a common base by folding significantly enhances design variety and is regularly occurring in liquid.

A Phosphine-ß-diketiminate Nickel(I)-Complex for Small Molecule Activation.

A bis(diphenyl)-phosphine functionalized ß-diketimine ligand (PNac-H) was applied for the synthesis of a subvalent Ni(I) complex [PNac-Ni]. Here, the Ni(I) center is stabilized by a tetradentate PNNP-type pocket, forming a square planar coordination sphere. Subsequently, the Ni(I) complex was investigated with regard to its reactivity and the activation of small molecules.

Luminescent early-late-hetero-tetranuclear group IV - Au(I) bisamidinate complexes.

The versatile metalloligand [{HCCC(NDipp)}Au] (dipp = 2,6-diisopropylphenyl) was converted into early-late heterotetrametallic complexes [{ClCpMCCC(NDipp)}Au] (M = Ti, Zr). These compounds show photoluminescence with either remarkably different (Ti) or similar (Zr) features as compared to related solely coinage metal containing acetylide amidinate complexes.

Tetra- and hexanuclear string complexes of the coinage metals.

Reaction of the PNNP ligand system ,'-bis[(2-diphenylphosphino)phenyl]formamidinate (dpfam) featuring different coordination compartments with [AuCl(tht)], [CuMes], [AgMes], or [AuCF(tht)] (tht = tetrahydrothiophene) resulted in tetranuclear homo- and heterometallic coinage metal complexes, as well as a hexanuclear gold complex. All of them feature a metal string conformation. Photophysical investigation revealed a significant dependence of the photoluminescence properties on the metal composition.

Molecular gold strings: aurophilicity, luminescence and structure-property correlations.

This review covers the compound class of one-dimensional gold strings. These compounds feature a formally infinite repetition of gold complexes as monomers/repeating units that are held together by aurophilic interactions, i.e.

Efficient Blue Phosphorescence in Gold(I)-Acetylide Functionalized Coinage Metal Bis(amidinate) Complexes.

The synthesis of linear symmetric ethynyl- and acetylide-amidinates of the coinage metals is presented. Starting with the desilylation of the complexes [{Me SiC≡CC(NDipp) } M ] (Dipp=2,6-diisopropylphenyl) (M=Cu, Au) it is demonstrated that this compound class is suitable to serve as a versatile metalloligand. Deprotonation with n-butyllithium and subsequent salt metathesis reactions yield symmetric tetranuclear gold(I) acetylide complexes of the form [{(PPh )AuC≡CC(NDipp) } M ] (M=Cu, Au).

A dimolybdenum paddlewheel as a building block for heteromultimetallic structures.

Diphenylphosphine functionalized propionic acid was applied for the synthesis of heteromultimetallic dimolybdenum(ii) complexes. The ligand features both carboxylic acid and phosphine functionalities, allowing the selective synthesis of a tetracarboxylate bridged Mo2(ii)-paddlewheel structure in a first step. Due to the symmetrically arranged phosphine functionalities, the dimolybdenum(ii) complex was utilized as a metalloligand.

Phosphine-substituted 1,2,3-triazoles as P,C- and P,N-ligands for photoluminescent coinage metal complexes.

A series of homo- and hetero-polynuclear coinage metal complexes based on a phosphine-substituted 1,2,3-triazole system is presented. Besides the P,N-ligand 1-benzyl-4-(diphenylphosphanyl)-1H-1,2,3-triazole (LPN), the P,C-donor ligand 1-benzyl-4-(diphenylphosphanyl)-3-methyl-1H-1,2,3-triazolium (LPCH+), featuring a potential mesoionic carbene moiety, was obtained by methylation of LPN. Starting from the monogold chloride complexes AuCl(LPN/LPC), the syntheses of a heterotrinuclear Au2Cu complex as well as a digold carbene complex are described.

Synthesis, Spectroscopy, and Redox Studies of Ferrocene-Functionalized Coinage Metal Alkyne Complexes.

Ethynylferrocene (FcC≡CH) was utilized as a redox-active metalloligand for the synthesis of polynuclear coinage metal complexes. The reaction of [FcC≡CLi] with tri- tert-butylphosphine metal chlorides [BuP-MCl] (M = Au, Ag, Cu) yielded different heteronuclear ferrocene-funtionalized alkyne complexes featuring metallophilic interactions. Furthermore, the redox properties of the ferrocenyl-functionalized tetracopper complex were investigated by cyclic voltammetry and UV-vis-near-IR spectroelectrochemistry.

Size Matters: From Two-Dimensional Au -Tl Metallopolymers to Molecular Complexes by Simple Variation of the Steric Demand.

Bis(acetylido) aurates(I) and thallium(I) trifluoromethylsulfonates were used to synthesize Au -Tl metallopolymers, displaying novel and unusual structural motifs of the metal-metal backbones in the solid state: a discrete molecular cluster, 1D chains of interconnected dimers, tetramers, or dodecamers of Au-Tl units, and a 2D-plane network, consisting of alternating edge-linked (AuTl) and (AuTl) cycles. The formation of the different architectures was primarily controlled by the steric demand of the acetylide-substituent groups. Thus, the bulkiest 2,6-diisopropylphenyl derivative yielded a molecular cluster [Tl Au ].

A highly luminescent octanuclear gold(i) carbide cluster.

The ligand [{MeSiC[triple bond, length as m-dash]CC(NDipp)}Li(thf)] (Dipp = 2,6-diisopropylphenyl) was used for salt metathesis reactions with [AuCl(tht)] (tht = tetrahydrothiophene) to obtain the dinuclear alkyne functionalized bisamidinate [{MeSiC[triple bond, length as m-dash]CC(NDipp)}Au]. This compound serves as a building block for the polynuclear carbide bridged gold(i) amidinate complex [Au{μ-(η:η-C[triple bond, length as m-dash]C)}(MeSiC[triple bond, length as m-dash]CC(NDipp))(tht)], which is the first gold(i) complex with a μ-η:η carbide coordination. Both gold(i) compounds show distinct aurophilic interactions and are remarkably stable at ambient conditions.

Periodontal conditions and incidence of new cardiovascular events among patients with coronary vascular disease.

Aim: We wanted to investigate whether periodontal conditions and/or oral care habits are associated with new cardiovascular events among patients with coronary vascular disease (CVD).

Materials And Methods: In this longitudinal cohort study, 1002 inpatients with CVD were included. They were examined regarding prevalence of severe periodontitis, bleeding upon probing (BOP), number of missing teeth and oral care habits.

SKINK: a web server for string kernel based kink prediction in α-helices.

Motivation: The reasons for distortions from optimal α-helical geometry are widely unknown, but their influences on structural changes of proteins are significant. Hence, their prediction is a crucial problem in structural bioinformatics. Here, we present a new web server, called SKINK, for string kernel based kink prediction.

The importance of genetic variants in TNFα for periodontal disease in a cohort of coronary patients.

Aim: The aim of this analysis was to evaluate the importance of genetic variants of TNFα for the severity of periodontal disease and periodontal risk factors with respect to periodontal risk factors in a cohort of coronary patients.

Subjects: A total of 942 consecutive patients with angiographic proven coronary heart disease were prospectively included in the study entitled "Periodontitis and Its Microbiological Agents as Prognostic Factors in Patients With Coronary Heart Disease" (ClinicalTrials.gov identifier:NCT01045070).

Obesity in a provincial population of Canadian preschool children: differences between 1984 and 1997 birth cohorts.

Objective: To determine whether trends of increasing overweight and obesity reported for older children and adults are evident in Canadian preschoolers.

Methods: A sample of 3857 preschool-aged children (51.1% boys) in the Province of Newfoundland and Labrador, born in 1984 and measured in 1987-1989, was selected from government archival records.

Anthropomorphic characteristics of centerfold models: trends towards slender figures over time.

Objective: Anthropomorphic characteristics of centerfold models were analyzed to determine if there has been a trend towards slimmer models over the last 50 years.

Method: Height and weight, breast, waist, and hip measurements of 559 Playboy centerfold models, obtained from the magazine's website, were analyzed.

Results: Regression analyses indicated a gradual and subtle change towards slimness.