Exploring Catalytic Intermediates in Pd-Catalyzed Aerobic Oxidative Amination of 1,3-Dienes: Multiple Metal Interactions of the Palladium Nanoclusters.

Metal nanoclusters (NCs) have unique properties because of their small size, which makes them useful as catalysts in reactions like cross-coupling. Pd-catalyzed oxidative amination, which involves dehydrogenative C-N bond formation, uses Pd complexes as the active species. It is known that the catalytic conditions involve the formation of Pd(0) species from Pd NCs, but the precise role of Pd NCs in the transformations has not been established. In this study, we investigated the characteristic properties of Pd NCs in oxidative amination of 1,3-dienes. The reaction achieved direct amination of commercially accessible 1,3-dienes with secondary aromatic amines, providing a variety of nitrogen containing 1,3-dienes. The compound was applicable to radical polymerization to provide the nitrogen-fabricated 1,3-diene-based polymer, which exhibited a different thermal stability compared to aliphatic nitrogen-fabricated diene polymers. In addition to the synthetic utility, by combining X-ray absorption fine structure and small-angle X-ray scattering analysis, we revealed amines and 1,3-dienes affected metal leaching from the Pd nanoparticles and stabilization of Pd NCs in the catalytic reaction. Additionally, DFT calculation suggested that the catalytic intermediate contained multiple adjacent Pd atoms and was responsible for formation of an σ-allylic intermediate that is difficult to form with the use of Pd complexes. These results could be used to understand the underlying phenomenon in the oxidative coupling reaction and develop Pd NCs-based dehydrogenation.

Sintering of Platinum-Containing Conjugated Polymers: Gas Adsorption and Catalysis of the Formed Pt-Carbon Composites.

Pt-containing meta- and para-linked poly(phenyleneethynylene)s were synthesized by the dehydrochlorination coupling polymerization of PtCl2(PBu3)2 with m- and p-diethynylbenzenes. The formed polymers were sintered at 900 °C to obtain Pt-graphene hybrids, whose structures were examined by Raman scattering spectroscopy, X-ray photoelectron spectroscopy (XPS), and X-ray diffraction (XRD) measurements. Shapes─facets, terraces, and steps─with average diameters of 2.0-3.4 µm were observed by field emission scanning electron microscopy (FE-SEM). The Pt-graphene hybrids moderately adsorbed CO2 and O2 and slightly adsorbed ethylene and methane. Epoxidation of stilbene was carried out using Pt-graphene hybrids as catalysts to obtain stilbene oxide.

Amino-Acid Based Chiral Trisubstituted Benzimidazole Supramolecules: Synthesis and Self-Assembling Behavior.

Trisubstituted 1,3,5-tri(benzimidazolyl)benzene derivatives were synthesized from l-alanine, l-valine, d-valine and glycine, and their self-assembling behavior and stimuli-response in solution and gel states were evaluated. Circular dichroism/UV-vis absorption spectroscopic and dynamic light scattering measurements revealed that the compounds formed H-aggregates via intramolecular hydrogen bonding and π-π stacking interactions in nonpolar solvents such as CHCl3, whereas collapse of the aggregates was confirmed by MeOH addition. Quantum mechanical calculations and molecular dynamics simulations also supported aggregation in CHCl3 . Rheological analysis and morphology observation revealed the formation of a fibril like structure by further assembling of aggregates at a high concentration in CHCl3 .

Photoluminescent supramolecular gels derived from phenylenediamine hydrochlorides.

Supramolecular gels are promising as chemosensors, drug delivery systems and oil gelators. The present paper deals with photoluminescent supramolecular gels derived from phenylenediamine hydrochlorides. N-(3,5-Diaminobenzoyl)-L-alanine dodecyl ester dihydrochlorides (1L) underwent gelation in tetrahydrofuran (THF) and CHCl3, but not in C1-C4 alcohols, dimethyl sulfoxide (DMSO) and N,N-dimethylformamide (DMF). Compound 1L emitted blue fluorescence in the sol state and green fluorescence in the gel state. A THF solution of 1L exhibited absorption and emission maxima at wavelengths 94-104 nm and 92-110 nm longer than those in other solvents, such as methanol and ethanol, that cause no gelation of 1L. Particles with hydrodynamic diameters around 13 nm were detected in a THF solution (c = 1.0 mM) of 1L. The gelation of 1L in THF and CHCl3, and the lack of gelation in MeOH were supported by molecular dynamics simulations and dynamic light scattering measurements. N-(3,5-Diaminobenzoyl)-L-alanine dodecyl ester (1L'), an HCl-free analogous compound of 1L, underwent no gelation in THF and CHCl3, indicating the necessity of the ammonium salt structure for gelation. The UV-vis absorption and photoluminescence spectroscopic peaks of 1L red-shifted upon aggregation, which was supported by TD-DFT calculations of monomeric and dimeric models of 1L.

Tyrosine-based photoluminescent diketopiperazine supramolecular aggregates.

L-Tyrosine diketopiperazine (DKP) derivative 1 was synthesized, and the aggregation and photoluminescence behaviors were examined. A solution of 1 in tetrahydrofuran (THF) gradually became viscous at room temperature, and turned into the gel state 5 hours after preparation, as confirmed by dynamic viscoelasticity measurement. A solution of 1 in THF exhibited photoluminescence. Fibrous patterns were observed by transmission electron, atomic force and fluorescence microscopies. Dynamic light scattering, semiempirical molecular orbital and density functional theory calculations, as well as molecular dynamics simulations, indicated aggregate formation. This was attributed to intermolecular hydrogen bonding, mainly between the DKP moieties and partly between the urethane moieties, resulting in π-orbital overlap of the terminal phenyl groups leading to photoluminescence.

Photoinduced formation of an azobenzene-based CD-active supramolecular cyclic dimer.

A series of new photo-responsive amino acid-derived azobenzenedicarboxylic acid derivatives (S)-1 a-e were synthesized. Compound (S)-1 a in the trans form exhibited no circular dichroism (CD) signal in DMF under ambient conditions, whereas intense Cotton effects were observed upon UV irradiation, indicating the formation of a chiral supramolecular structure in the cis form. The CD signals disappeared when trifluoroacetic acid (TFA) was added to the solution. The ester counterpart [(S)-1 a'] showed no CD signal. Hydrogen bonding between the carboxy groups seemed necessary for constructing the supramolecular structure. The kinetic studies of cis to trans isomerization of (S)-1 a demonstrated that the formation of a chiral supramolecule enhances the stability of the cis-azobenzene structure. The ESI mass spectrum of stilbenedicarboxylic acid (S)-4, an analogue of (S)-1 b, confirmed the formation of a dimer. A theoretical CD study revealed that (S)-1 a in the cis form should be present as a cyclic chiral dimer.

Synthesis and helical structures of poly(ω-alkynamide)s having chiral side chains: effect of solvent on their screw-sense inversion.

New ω-alkynamides, (S)-HC≡CCH2CONHCH2CH(CH3)CH2CH3 (1) and (S)-HC≡CCH2CH2CONHCH(CH3)CH2CH2CH2CH2CH3 (2) were synthesized and polymerized with a rhodium catalyst in CHCl3 to obtain cis-stereoregular poly(ω-alkynamide)s (poly(1) and poly(2)). Polarimetric, CD, and IR spectroscopic studies revealed that in solution the polymers adopted predominantly one-handed helical structures stabilized by intramolecular hydrogen bonds between the pendent amide groups. This behavior was similar to that of the corresponding poly(N-alkynylamide) counterparts (poly(3) and poly(4)) reported previously, whereas the helical senses were opposite to each other. The helical structures of the poly(ω-alkynamide)s were stable upon heating similar to those of the poly(N-alkynylamide)s, but the solvent response was completely different. An increase in MeOH content in CHCl3/MeOH resulted in inversion of the predominant screw-sense for poly(1) and poly(2). Conversely, poly(3) was transformed into a random coil, and poly(4) maintained the predominant screw-sense irrespective of MeOH content. The solvent dependence of predominant screw-sense for poly(1) and poly(2) was reasonably explained by molecular orbital studies using the conductor-like screening model (COSMO).

Synthesis of a platinacycle: determination of the structure and examination of the photophysical properties based on DFT calculations.

Platinum-containing macrocycles (platinacycles) have gained attention due to their unique photoelectric properties. In the present study, a novel conjugated platinacycle was synthesized by the dehydrochlorination coupling reaction of a bipyridine dichloroplatinum(II) complex and a 3,6-diethynylcarbazol derivative. The structure of the platinacycle was confirmed by 1H/13C, 1H-1H COSY, HMQC, HMBC, DEPT NMR spectroscopies in conjunction with DFT calculations, IR spectroscopy and MALDI-TOF mass spectrometry. The platinacycle exhibited a UV-vis absorption around 540 nm assignable to ligand-ligand charge transfer, and birefringence in DMF, possibly due to alignment of molecules.

Synthesis of end-functionalized polyacetylenes that contain polar groups by employing well-defined palladium catalysts.

A series of [(dppf)PdBr(R)]-type complexes (dppf=1,1'-bis(diphenylphosphino)ferrocene; R=p-cyanophenyl (1 a), o-hydroxymethylphenyl (1 b), and triphenylvinyl (1 c)), in combination with silver trifluoromethanesulfonate (AgOTf), were demonstrated to be active for the polymerization of monosubstituted polar acetylene monomers HC≡CCONHC(4)H(9) (2), HC≡CCO(2)C(8)H(17) (3), HC≡CCH(2)OCONHC(6)H(13) (4), HC≡CCH(2)OCO(2)C(6)H(13) (5), and HC≡CCH(CH(3))OH (6). The yields and molecular weights of the polymers depended on the combination of the Pd catalyst and monomer that was employed. Matrix-assisted laser-desorption/ionization-time of flight (MALDI-TOF) mass spectrometric analysis indicated the formation of polymers that contained the "R" and "H" groups at the chain ends. IR spectroscopic analysis supported the R-end-functionalization of the polymers. NMR spectroscopy and MS identified the presence of species that were formed by single, double, and triple insertion of the monomers into the Pd-C(6)H(4)-p-CN bond, thereby giving solid evidence for an insertion mechanism for the present system. Density functional theory (DFT) calculations suggested the preference for 1,2-insertion of the monomer compared to 2,1-insertion.

Alternating ring-opening metathesis copolymerization of amino acid derived norbornene monomers carrying nonprotected carboxy and amino groups based on acid-base interaction.

Amino acid derived norbornene monomers having carboxy (1) and amino groups (2) were synthesized and subjected to ring-opening metathesis copolymerization with various feed ratios using the Grubbs second generation ruthenium catalyst. The M(n)'s of the copolymers ranged from 5300 to 9400 (M(w)/M(n) = 1.40-1.69). The monomer conversion and M(n) of the copolymer were maximized when the monomer feed ratio was 1:1. The monomer unit ratios in the copolymers were almost 1:1 at 10% conversion, irrespective of the feed ratios. The monomer reactivity ratios r(1) and r(2) were estimated to be 0.08 and 0.02, which confirmed that alternating copolymerization occurred. It is considered that alternating copolymerization is brought about by the acid-base interaction between the monomers and/or between the propagating polymer end and the incoming monomer.

Synthesis and extremely high gas permeability of polyacetylenes containing polymethylated indan/tetrahydronaphthalene moieties.

Polymethylated poly(diphenylacetylene) derivatives, a new category of substituted polyacetylenes, were successfully synthesized, and proved to show extremely high gas permeability.

Controlled monomer insertion into polymer main chain: synthesis of sequence ordered polystyrene containing thiourethane and trithiocarbonate units by the RAFT process.

A polymer having a trithiocarbonate moiety in the main chain was applied as a polymeric precursor to the synthesis of a sequence ordered polymer by insertion polymerization of styrene into the main chain by a RAFT mechanism.

Helical polymer carrying helical grafts from peptide-based acetylene macromonomers: synthesis.

N-Propargylamide-terminated peptide-based macromonomers with a degree of polymerization ranging from 4 to 40 were synthesized by the polymerization of gamma-benzyl and gamma-stearyl-L-glutamate-N-carboxy anhydrides initiated with propargylamine. The macromonomers took an alpha-helical structure, which was confirmed by signals at 208 and 220 nm in CD spectra. The macromonomers were subjected to polymerization and copolymerization with an alanine-derived N-propargylamide [N-(tert-butoxycarbonyl)-L-alanine-N'-propargylamide] catalyzed with (2,5-norbornadiene)Rh+[eta6-C6H5B- (C6H5)3]. It was confirmed through a CD spectroscopic study that the copolymer obtained from the copolymerization of the gamma-stearyl-L-glutamate-based macromonomer with the alanine-derived N-propargylamide had a helical polyacetylene main chain and helical polypeptide side chains.

New Approach to the Polymerization of Disubstituted Acetylenes by Bulky Monophosphine-Ligated Palladium Catalysts.

Bulky monophosphine-ligated Pd complexes served as unprecedented admirable catalysts for the polymerization of a disubstituted acetylene. The moderately high polymer yields and cis content of the formed polyacetylene contrasted with those observed for traditional Mo catalyst-based polymer. These Pd catalysts are strong tools to promote the understanding of the structure-property relationships of disubstituted acetylenes.

Synthesis and helical structure of poly(1-methylpropargyl ester)s with various side chains.

Optically active 1-methylpropargyl esters bearing various substituents were polymerized with [(nbd)Rh](+)[eta(6)-C(6)H(5)B(C(6)H(5))(3)](-) (nbd=norbornadiene) as a catalyst to afford the corresponding poly(1-methylpropargyl ester)s with moderate molecular weights in good yields. The polymers have a cis-stereoregular structure, which was determined by (1)H NMR spectroscopy. Large optical rotations and clear CD signals demonstrated that all these polymers take on a helical structure with a predominantly one-handed screw sense. The polymers exhibited large viscosity indices in the range 1.14-1.75. Chiral amplification was observed in R/S copolymerization. Conformational analysis revealed that the polymers form a tightly twisted helical structure with a dihedral angle of 70 degrees at the single bond of the main chain.

Control of helix sense by composition of chiral-achiral copolymers of N-propargylbenzamides.

N-Propargylbenzamides 1-7 were polymerized with (nbd)Rh(+)[eta(6)-C(6)H(5)B(-)(C(6)H(5))(3)] to afford polymers with moderate molecular weights (M(n) = 26,000-51,000) in good yields. The (1)H NMR spectra demonstrated that the polymers have fairly stereoregular structures (81-88 % cis). The optically active polymers, poly(1) and poly(2), were proven by their intense CD signals and large optical rotations to adopt a stable helical conformation with an excess of one-handed screw sense when heated in CHCl(3) or toluene. The sign of Cotton effect could be controlled by varying the content in the copolymers of either chiral bulky 1 and achiral nonbulky 3, or chiral nonbulky 2 and achiral bulky 7. The smaller the pendant group in the copolymerization of achiral monomers with 1, the more easily did the preferential helical sense change with the copolymer composition. However, the copolymers of chiral nonbulky 2 and achiral nonbulky 3 did not change the helical sense, irrespective of the composition. The free energy differences between the plus and minus helical states, as well as the excess free energy of the helix reversal, of those chiral-achiral random copolymers were estimated by applying a modified Ising model.