Deep-red photoluminescent mechanoresponsive polymers with dynamic Cu-arylamide mechanophores.

We demonstrate the use of copper arylamide complexes as efficient photoluminescent mechanophores to design deep-red/near-IR emissive polymers showing reversible changes in photoluminescence intensity in the red/near-IR region in response to mechanical stretching. The mechanoresponse was repeatable over 30 cycles, showing a measurable increase of photoluminescence intensity even at a small applied stress of 0.01 MPa.

A new species of Karekizo Morimoto, 1962 (Coleoptera: Curculionidae: Molytinae) from the Alishan Mountains of Taiwan and a first record of Karekizo impressicollis outside Japan.

Karekizo Morimoto, 1962 represents a rarely collected, mountain-dwelling genus which has hitherto been known only from one species, K. impressicollis Morimoto, 1962, in Japan. Here, a second species, Karekizo depressus sp.

Oxygen transfer reactivity mediated by nickel perfluoroalkyl complexes using molecular oxygen as a terminal oxidant.

Nickel perfluoroethyl and perfluoropropyl complexes supported by naphthyridine-type ligands show drastically different aerobic reactivity from their trifluoromethyl analogs resulting in facile oxygen transfer to perfluoroalkyl groups or oxygenation of external organic substrates (phosphines, sulfides, alkenes and alcohols) using O or air as a terminal oxidant. Such mild aerobic oxygenation occurs through the formation of spectroscopically detected transient high-valent Ni and structurally characterized mixed-valent Ni-Ni intermediates and radical intermediates, resembling O activation reported for some Pd dialkyl complexes. This reactivity is in contrast with the aerobic oxidation of naphthyridine-based Ni(CF) complexes resulting in the formation of a stable Ni product, which is attributed to the effect of greater steric congestion imposed by longer perfluoroalkyl chains.

Heterometallic bond activation enabled by unsymmetrical ligand scaffolds: bridging the opposites.

Heterobi- and multimetallic complexes providing close proximity between several metal centers serve as active species in artificial and enzymatic catalysis, and in model systems, showing unique modes of metal-metal cooperative bond activation. Through the rational design of well-defined, unsymmetrical ligand scaffolds, we create a convenient approach to support the assembly of heterometallic species in a well-defined and site-specific manner, preventing them from scrambling and dissociation. In this perspective, we will outline general strategies for the design of unsymmetrical ligands to support heterobi- and multimetallic complexes that show reactivity in various types of heterometallic cooperative bond activation.

Synthesis of zigzag- and fjord-edged nanographene with dual amplified spontaneous emission.

We report the synthesis of a dibenzodinaphthocoronene (DBDNC) derivative as a novel nanographene with armchair, zigzag, and fjord edges, which was characterized by NMR and X-ray crystallography as well as infrared (IR) and Raman spectroscopies. Ultrafast transient absorption (TA) spectroscopy revealed the presence of stimulated emission signals at 655 nm and 710 nm with a relatively long lifetime, which resulted in dual amplified spontaneous emission (ASE) bands under ns-pulsed excitation, indicating the promise of DBNDC as a near-infrared (NIR) fluorophore for photonics. Our results provide new insight into the design of nanographene with intriguing optical properties by incorporating fjord edges.

Ligand-free nickel catalyzed perfluoroalkylation of arenes and heteroarenes.

We describe a "ligand-free" Ni-catalyzed perfluoroalkylation of heteroarenes to produce a diverse array of trfiluoromethyl, pentafluoroethyl and heptafluoropropyl adducts. Catalysis proceeds at room temperature a radical pathway. The catalytic protocol is distinguished by its simplicity, and its wide scope demonstrates the potential in the late-stage functionalization of drug analogues and peptides.

On the melting point depression, coalescence, and chemical ordering of bimetallic nanoparticles: the miscible Ni-Pt system.

Among the properties that distinguish nanoparticles (NPs) from their bulk counterparts is their lower melting points. It is also common knowledge that relatively low melting points enhance the coalescence of (usually) nascent nanoclusters toward larger NPs. Finally, it is well established that the chemical ordering of bi- (or multi-) metallic NPs can have a profound effect on their physical and chemical properties, dictating their potential applications.

Direct observation of reversible bond homolysis by 2D EXSY NMR.

Bond homolysis is one of the most fundamental bond cleavage mechanisms. Thus, understanding of bond homolysis influences the development of a wide range of chemistry. Photolytic bond homolysis and its reverse process have been observed directly using time-resolved spectroscopy.

Construction of modular Pd/Cu multimetallic chains ligand- and anion-controlled metal-metal interactions.

The presence of Pd⋯Cu and Pd⋯Pd interactions as well as the order of metal atoms in a chain held by a modular polynucleating ligand is controlled by the coordinating ability of the anions, leading to selective formation of bi- and tetranuclear Pd/Cu and Pd chains. Metal-metal cooperative reactivity in these complexes was tested in Ar-O bond formation and alkyne activation.

Metal-metal cooperative bond activation by heterobimetallic alkyl, aryl, and acetylide Pt/Cu complexes.

We report the selective formation of heterobimetallic Pt/Cu complexes that demonstrate how facile bond activation processes can be achieved by altering the reactivity of common organoplatinum compounds through their interaction with another metal center. The interaction of the Cu center with the Pt center and with a Pt-bound alkyl group increases the stability of PtMe towards undesired rollover cyclometalation. The presence of the Cu center also enables facile transmetalation from an electron-deficient tetraarylborate [B(Ar)] anion and mild C-H bond cleavage of a terminal alkyne, which was not observed in the absence of an electrophilic Cu center.

Tuning the coalescence degree in the growth of Pt-Pd nanoalloys.

Coalescence is a phenomenon in which two or more nanoparticles merge to form a single larger aggregate. By means of gas-phase magnetron-sputtering aggregation experiments on Pt-Pd nanoalloys, it is shown that the degree of coalescence can be tuned from a growth regime in which coalescence is negligible to a regime where the growth outcome is dominated by coalescence events. This transition is achieved by varying both the length of the aggregation zone and the pressure difference between the aggregation and the deposition chamber.

Proton-responsive naphthyridinone-based Ru complexes and their reactivity with water and alcohols.

We report the synthesis and reactivity of RuII complexes with a new naphthyridinone-substituted phosphine ligand, 7-(diisopropylphosphinomethyl)-1,8-naphthyridin-2(1H)-one (L-H), which contains two reactive sites that can potentially be deprotonated by a strong base: an NH proton of naphthyridinone and a methylene arm attached to the phosphine. In the absence of a base, the stable bis-ligated complex Ru(L-H)2Cl2 (1) containing two NH groups in the secondary coordination sphere is formed. Upon further reaction with a base, a doubly deprotonated, dimeric complex is obtained, [Ru2(L*-H)2(L)2] (2), in which two of the four ligands undergo deprotonation at the NH (L), while the other two ligands are deprotonated at the methylene groups (L*-H) as confirmed by an X-ray diffraction study; intramolecular hydrogen bonding is present between the NH group of one ligand and an O-atom of another ligand in the dimeric structure, which stabilizes the observed geometry of the complex.

Coupled Spin States in Armchair Graphene Nanoribbons with Asymmetric Zigzag Edge Extensions.

Exact positioning of sublattice imbalanced nanostructures in graphene nanomaterials offers a route to control interactions between induced local magnetic moments and to obtain graphene nanomaterials with magnetically nontrivial ground states. Here, we show that such sublattice imbalanced nanostructures can be incorporated along a large band gap armchair graphene nanoribbon on the basis of asymmetric zigzag edge extensions, achieved by incorporating specifically designed precursor monomers. Scanning tunneling spectroscopy of an isolated and electronically decoupled zigzag edge extension reveals Hubbard-split states in accordance with theoretical predictions.

Overcoming Steric Hindrance in Aryl-Aryl Homocoupling via On-Surface Copolymerization.

On-surface synthesis is a unique tool for growing low-dimensional carbon nanomaterials with precise structural control down to the atomic level. This novel approach relies on carefully designed precursor molecules, which are deposited on suitable substrates and activated to ultimately form the desired nanostructures. One of the most applied reactions to covalently interlink molecular precursors is dehalogenative aryl-aryl coupling.

Breaking out of biogeographical modules: range expansion and taxon cycles in the hyperdiverse ant genus .

Aim: We sought to reconstruct the biogeographical structure and dynamics of a hyperdiverse ant genus, and to test several predictions of the taxon cycle hypothesis. Using large datasets on geographical distributions and phylogeny, we (1) inferred patterns of biogeographical modularity (clusters of areas with similar faunal composition), (2) tested whether species in open habitats are more likely to be expanding their range beyond module boundaries, and (3) tested whether there is a bias of lineage flow from high- to low-diversity areas.

Location: The Old World.

Unexpectedly complex gradation of coral population structure in the Nansei Islands, Japan.

To establish effective locations and sizes of potential protected areas for reef ecosystems, detailed information about source and sink relationships between populations is critical, especially in archipelagic regions. Therefore, we assessed population structure and genetic diversity of Acropora tenuis, one of the dominant stony coral species in the Pacific, using 13 microsatellite markers to investigate 298 colonies from 15 locations across the Nansei Islands in southwestern Japan. Genetic diversity was not significant among sampling locations, even in possibly peripheral locations.

Genetic differentiation and connectivity of morphological types of the broadcast-spawning coral Galaxea fascicularis in the Nansei Islands, Japan.

Population connectivity resulting from larval dispersal is essential for the maintenance or recovery of populations in marine ecosystems, including coral reefs. Studies of species diversity and genetic connectivity within species are essential for the conservation of corals and coral reef ecosystems. We analyzed mitochondrial DNA sequence types and microsatellite genotypes of the broadcast-spawning coral, Galaxea fascicularis, from four regions in the subtropical Nansei Islands in the northwestern Pacific Ocean.