Transition metal ion-modified polyurethanes: Spectroscopic and thermal studies on polyesterurethane/chromium metallopolymers

Polyesterurethane/chromium(III) metallopolymers (PUCr) having chromium contents below 1% were prepared by using different initial molar ratios urethane groups/chromium ions. PUCr were characterized in comparison with the parent polyurethane (PU) by AAS, UV-Vis absorption spectroscopy, FTIR spectroscopy, DSC, DMA and TGA. Chromium ions form coordination complexes with the urethane nitrogen atoms, the intermolecular complexation bringing about the crosslinking of the hard segments. As a result, disturbance of the hydrogen bonding and modifications in the crystallinity of the hard-segment domains take place. PUCr exhibit higher values of soft-segment glass transition and storage modulus than PU, revealing the reinforcing effect of chromium ions on the polyurethane matrix. As compared with PU, PUCr present lower initial thermal stability, a strongly catalyzed final stage of the thermal decomposition process and more thermally stable intermediate decomposition products.     

A conformation study of polyelectrolyte-dendritic surfactant complexes in dilute solutions

<正>Three dendronized polymers from generation one to generation three have been prepared by complexing negatively charged Frechet-type dendrons with a polyanion,poly(diallydimethylammonium chloride)(PDADMAC).The grafting degree has been confirmed mainly by elemental analysis.In dilute solutions of tetrahydrofuran,static light scattering studies indicate that the first generation complex has a coil-like conformation,even more flexible than PDADMAC.The second and third generation complexes exhibit polyelectrolyte behavior.Dynamic light scattering experiments indicate that all the three complexes have almost the same hydrodynamic radius,indicating that they might own similar coil conformation.Atomic force microscopy shows the existence of disordered globules formed by one or a couple of complex coils.All these observations can be explained by the flowerlike coil conformation,which is formed by the intra-molecular association.This is totally different from the stretched chain conformation formed by covalently connected dendronized polymers.This result also explains why some ordered supramolecular structures,found in condensed state of the similar complexes,are not as perfect as those of conventional dendronized polymers.     

NO donors cis-[Ru(bpy)2(L)NO] and [Fe(CN)4(L)NO] complexes immobilized on modified mesoporous silica spheres

The reaction of [Ru(bpy)₂Cl₂] and Na₂[Fe(CN)₄(dmso)₂] complexes with isonicotinic acid immobilized on silica spheres (Si-ATPS-ISN) followed by a NO bubbling produced Si-ATPS-ISN-[Ru(bpy)₂(NO)] (system I) and Si-ATPS-ISN-[Fe(CN)₄(NO)] (system II). The characterization of these systems was carried out by UV–Vis, FTIR spectroscopy and electrochemical techniques. As judged by the FTIR data, the nitric oxide ligand has an NO⁺ character in both systems (ν(NO⁺): 1938 cm⁻¹). The NO release, which was monitored by means of FTIR, electrochemistry, and NO sensor electrode, was observed for both systems upon white light irradiation and chemical reduction by cysteine. These results indicated that the system (II) presents a higher potential for controlled NO release. The characterization (FTIR and UV–Vis) of the systems after the NO release suggested the formation of the aqua systems ATPS-ISN-[Ru(bpy)₂(OH₂)] and ATPS-ISN-[Ru(bpy)₂(OH₂)].     

Complexes of directed trees and independence complexes

First we prove that certain complexes on directed acyclic graphs are shellable. Then we study independence complexes. Two theorems used for breaking and gluing such complexes are proved and applied to generalize the results by Kozlov.An interesting special case is anti-Rips complexes: a subset P of a metric space is the vertex set of the complex, and we include as a simplex each subset of P with no pair of points within distance r. For any finite subset P of R the homotopy type of the anti-Rips complex is determined.     

Revealing Excited-State Trajectories on Potential Energy Surfaces with Atomic Resolution in Real Time

Photoexcited molecular trajectories on potential energy surfaces (PESs) prior to thermalization are intimately connected to the photochemical reaction outcome. The excited-state trajectories of a diplatinum complex featuring photo-activated metal–metal σ-bond formation and associated Pt−Pt stretching motions were detected in real time using femtosecond wide-angle X-ray solution scattering. The observed motions correspond well with coherent vibrational wavepacket motions detected by femtosecond optical transient absorption. Two key coordinates for intersystem crossing have been identified, the Pt−Pt bond length and the orientation of the ligands coordinated with the platinum centers, along which the excited-state trajectories can be projected onto the calculated PESs of the excited states. This investigation has gleaned novel insight into electronic transitions occurring on the time scales of vibrational motions measured in real time, revealing ultrafast nonadiabatic or non-equilibrium processes along excited-state trajectories involving multiple excited-state PESs.     

Noncovalent Modulation of Chemoselectivity in the Gas Phase Leads to a Switchover in Reaction Type from Heterolytic to Homolytic to Electrocyclic Cleavage

In the gas phase, thermal activation of supramolecular assemblies such as host–guest complexes leads commonly to noncovalent dissociation into the individual components. Chemical reactions, for example of encapsulated guest molecules, are only found in exceptional cases. As observed by mass spectrometry, when 1-amino-methyl-2,3-diazabicyclo[2.2.2]oct-2-ene (DBOA) is complexed by the macrocycle β-cyclodextrin, its protonated complex undergoes collision-induced dissociation into its components, the conventional reaction pathway. Inside the macrocyclic cavity of cucurbit[7]uril (CB7), a competitive chemical reaction of monoprotonated DBOA takes place upon thermal activation, namely a stepwise homolytic covalent bond cleavage with the elimination of N₂, while the doubly protonated CB7⋅DBOA complex undergoes an inner-phase elimination of ethylene, a concerted, electrocyclic ring-opening reaction. These chemical reaction pathways stand in contrast to the gas-phase chemistry of uncomplexed monoprotonated DBOA, for which an elimination of NH₃ predominates upon collision-induced activation, as a heterolytic bond cleavage reaction. The combined results, which can be rationalized in terms of organic-chemical reaction mechanisms and density-function theoretical calculations, demonstrate that chemical reactions in the gas phase can be steered chemoselectively through noncovalent interactions.     

Bonding and Reactivity in Terminal versus Bridging Arenide Complexes of Thorium Acting as ThII Synthons

Thorium redox chemistry is extremely scarce due to the high stability of Th^IV. Here we report two unique examples of thorium arenide complexes prepared by reduction of a Th^IV-siloxide complex in presence of naphthalene, the mononuclear arenide complex [K(OSi(O^tBu)₃)₃Th(η⁶-C₁₀H₈)] ( 1 ) and the inverse-sandwich complex [K(OSi(O^tBu)₃)₃Th]₂(μ-η⁶,η⁶-C₁₀H₈)] ( 2 ). The electrons stored in these complexes allow the reduction of a broad range of substrates (N₂O, AdN₃, CO₂, HBBN). Higher reactivity was found for the complex 1 which reacts with the diazoolefin IDipp=CN₂ to yield the unexpected Th^IV amidoalkynyl complex 5 via a terminal N-heterocyclic vinylidene intermediate. This work showed that arenides can act as convenient redox-active ligands for implementing thorium-ligand cooperative multielectron transfer and that the reactivity can be tuned by the arenide binding mode.     

Diazoalkenes: From an Elusive Intermediate to a Stable Substance Class in Organic Chemistry

Over decades diazoalkenes (R₂C=C=N₂) were postulated as reactive intermediates in organic chemistry even though their direct spectroscopic detection proved very challenging. In the 1970/80ies several groups probed their existence mainly indirectly by trapping experiments or directly by matrix-isolation studies. In 2021, our group and the Severin group reported independently the synthesis and characterization of the first room-temperature stable diazoalkenes, which initiated a rapidly expanding research field. Up to now four different classes of N-heterocyclic substituted room-temperature stable diazoalkenes have been reported. Their properties and unique reactivity, such as N₂/CO exchange or utilization as vinylidene precursors in organic and transition metal chemistry are presented. This review summarizes the early discoveries of diazoalkenes from their initial postulation as transient, elusive species up to the recent findings of the room-temperature stable derivatives.     

Taming of Furfurylidenes by Chiral Bismuth-Rhodium Paddlewheel Catalysts. Preparation and Functionalization of Optically Active 1,1-Disubstituted (Trifluoromethyl)cyclopropanes

Although 2-furyl-carbenes (furfurylidenes) are prone to instantaneous electrocyclic ring opening, chiral [BiRh]-paddlewheel complexes empowered by London dispersion allow (trifluoromethyl)furfurylidene metal complexes to be generated from a bench-stable triftosylhydrazone precursor. These reactive intermediates engage in asymmetric [2+1] cycloadditions and hence open entry into valuable trifluoromethylated cyclopropane or -cyclopropene derivatives in optically active form, which are important building blocks for medicinal chemistry but difficult to make otherwise.     

Selective Separation of Lithium,Magnesium and Calcium using 4-Phosphoryl Pyrazolones as pH-Regulated Receptors

Ensuring continuous and sustainable lithium supply requires the development of highly efficient separation processes such as LLE (liquid-liquid extraction) for both primary sources and certain waste streams. In this work, 4-phosphoryl pyrazolones are used in an efficient pH-controlled stepwise separation of Li⁺ from Ca²⁺, Mg²⁺, Na⁺ and K⁺. The factors affecting LLE process, such as the substitution pattern of the extractant, diluent/water distribution, co-ligand, pH, and speciation of the metal complexes involved, were systematically investigated. The maximum extraction efficiency of Li⁺ at pH 6.0 was 94 % when Mg²⁺ and Ca²⁺ were previously separated at pH<5.0, proving that the separation of these ions is possible by simply modulating the pH of the aqueous phase. Our study points a way to separation of lithium from acid brine or from spent lithium ion battery leaching solutions, which supports the future supply of lithium in a more environmentally friendly and sustainable manner.