Photoinduced axial ligation and deligation dynamics of nonplanar nickel dodecaarylporphyrins

The ground- and excited-state metal-ligand dynamics of nonplanar nickel(II) 2,3,5,7,8,10,12,13,15,17,18,20-dodecaphenylporphyrin (NiDPP) and two fluorinated analogues (NiF(20)DPP and NiF(28)DPP) have been investigated using static and time-resolved absorption spectroscopy in toluene and in ligating media that differ in basicity, aromaticity, and steric encumbrance. Because of the electronic and steric consequences of nonplanarity, NiDPP does not bind axial ligands in the ground state, but metal coordination does occur after photoexcitation with multistep dynamics that depend on the properties of the ligand. Following the structural relaxations that occur in all nickel porphyrins within approximately 10 ps, ligand binding to photoexcited NiDPP is progressively longer in pyridine, piperidine, and 3,5-lutidine (25-100 ps) but does not occur at all in 2,6-lutidine in which the ligating nitrogen is sterically encumbered. The transient intermediate that is formed, which nominally could be either a five- or six-coordinate species, also has a ligand-dependent lifetime (200-550 ps). Decay of this intermediate occurs partially via ligand release to re-form the uncoordinated species, in competition with binding of the second axial ligand and/or conformational/electronic relaxations (of a six-coordinate intermediate) to give the ground state of the bis-ligated photoproduct. The finding that the photoproduct channel principally depends on ligand characteristics along with the time-evolving spectra suggests that the transient intermediate may involve a five-coordinate species. In contrast to NiDPP, the fluorinated analogues NiF(20)DPP and NiF(28)DPP do coordinate axial ligands in the ground state but eject them after photoexcitation. Collectively, these results demonstrate the sensitivity with which the electronic and structural characteristics of the macrocycle, substituents, and solvent (ligands) can govern the photophysical and photochemical properties of nonplanar porphyrins and open new avenues for exploring photoinduced ligand association and dissociation behavior.     

The fluoro analogue of Wilkinson's catalyst and unexpected Ph-Cl activation

The fluoro analogue of Wilkinson's catalyst, [(Ph3P)3RhF] (1), was synthesized and fully characterized. Both solution behavior and solid-state geometry parameters of 1 were found to be surprisingly similar to those of Wilkinson's catalyst. Unlike Wilkinson's catalyst however, 1 exhibited most unusual reactivity toward the notoriously inert C-Cl bond of nonactivated chloroarenes. The novel Ph-Cl activation with 1 includes fluorine transfer from the metal to a phosphine ligand and evidently phenyl transfer from the phosphine to Rh to produce an electron-rich sigma-phenylrhodium intermediate.     

Transition metal complexes with thiosemicarbazide-based ligands,IV: Synthesis and molecular structure of 5-nitrosalicylaldehyde S-methylisothiosemicarbazonato-piperidine-copper(II)

Summary The reaction of warmDMF solutions of Cu(II) perchlorate, 5-nitrosalicylaldehyde S-methylisothiosemicarbazone (H₂ L) and piperidine (Pip) yielded the paramagnetic (_eff=2.19 B.M.) Cu(L)Pip complex, whereL is the dianionic form of H₂ L, formed as a result of deprotonation of the phenolic hydroxyl and NH₂ group. Crystal data of the complex are: monoclinic P2₁,a=11.902(4),b=6.765(3),c=11.343(4)Å; =112.92°,V=841.20(8)ų,M=400.9,Z=2,d ₀=1.60 gcm^–3,d _c =1.58 gcm^–3,F(000)=424. The structure was refined to a residualR=0.047. The copper(II) ion is coordinated in a square-planar arrangement by the piperidine nitrogen and the NNO set of donor atoms ofL.

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Komplexe der Übergangsmetalle mit Thiosemicarbazid-Liganden, IV. Synthese und molekulare Struktur von 5-Nitrosalicylaldehyd-S-methylisothiosemicarbazonato-piperidin-kupfer(II)

Zusammenfassung Durch die Reaktion in warmenDMF-Lösungen von Cu(II) Perchlorat, 5-Nitrosalicylaldehyd-S-methylisothiosemicarbazon (H₂ L) und Piperidin (Pip) wurde ein paramagnetischer Komplex (_eff=2.19 B.M.) Cu(L)Pip erhalten, wobeiL nach doppelter Deprotonierung (NH₂- und Phenolhydroxyl-Gruppe) als dianionische Form von H₂ L vorliegt. Die kristallographischen Daten des Komplexes sind: monokline Raumgruppe P2₁,a=11.902(4),b=6.765(3),c=11.343(4)Å, =112.92°;V=841.20ų,M=400.9,Z=2,d ₀=1.60 gcm^–3,d _c =1.58 gcm^–3,F(000)=424. Die struktur wurde bis zu einemR-Wert von 0.047 verfeinert. Die Koordination des Kupfers wird quadratisch-planar über den Piperidin-Stickstoff und die NNO-Donorhülle der Chelatliganden gebildet.

     

The alicyclic ring contraction of perfluoro-1-phenyltetralin in reaction with antimony pentafluoride

Perfluoro-1-phenyltetralin (1) heated with antimony pentafluoride at 130 °C, then treated with water, gave a mixture of perfluorinated 3-methyl-2-phenylindenone (3), 3-methyl-2-phenylindene (4), 3-hydroxy-1-methyl-3-phenylindan (5), 1-methyl-3-phenylindan (6), 9-methyl-1,2,3,4,5,6,7,8-octahydroanthracene (7), and 1,9-dimethyl-5,6,7,8-tetrahydro-β-naphthindan (8). When heated with SbF₅ in the presence of HF, then treated with water, compound 1 is transformed to a mixture of products 3-6. The reaction at 170 and 200 °C forms compounds 3-6 together with perfluoro-2-(cyclohexen-1-yl)-3-methylindene (10).     

Corrected results for the influence of size,zeta potential,and state of motion of dispersed particles on the conductivity of a colloidal suspension

A correction of a recent work on the dependence of the DC conductivity of diluted colloidal suspensions on the size, zeta potential, and state of motion of dispersed particles (C. Grosse, S. Pedrosa, V.N. Shilov, J. Colloid Interface Sci. 251 (2002) 304) is presented. It is shown that the procedure used in that work to calculate the contribution of the particles to the conductivity of the suspension leads to a result that includes the variation of the conductivity of the dispersion medium. Revised analytical and numerical calculations are presented, which strongly reinforce the conclusions reached in the original work: The expression for the conductivity increment based on the value of the dipolar coefficient of the suspended particles (calculated taking into account their electrophoretic motion) appears to be valid over the whole range of particle sizes.     

Effects of Added Surfactant on the Dynamic Interfacial Tension Behavior of Acidic Oil/Alkaline Systems

The effects of a ready-made surfactant (sodium dodecyl sulfate) on the dynamic interfacial tension between a model acidic oil (linoleic acid dissolved in paraffin oil) and various aqueous alkaline (NaOH) systems have been studied using pendant drop tensiometry at surfactant concentrations both below and above the critical micelle concentration (CMC). Below the CMC the added surfactant contributes significantly to a further reduction of interfacial tension of the reacting acid/alkaline system, whereas above the CMC the added surfactant plays an important role in damping the dynamic trends observed for the reactive system alone. Copyright 2001 Academic Press.     

Network manipulation algorithm based on inexact alternating minimization

In this paper, we present a network manipulation algorithm based on an alternating minimization scheme from Nesterov (Soft Comput 1–12, 2020). In our context, the alternative process mimics the natural behavior of agents and organizations operating on a network. By selecting starting distributions, the organizations determine the short-term dynamics of the network. While choosing an organization in accordance with their manipulation goals, agents are prone to errors. This rational inattentive behavior leads to discrete choice probabilities. We extend the analysis of our algorithm to the inexact case, where the corresponding subproblems can only be solved with numerical inaccuracies. The parameters reflecting the imperfect behavior of agents and the credibility of organizations, as well as the condition number of the network transition matrix have a significant impact on the convergence of our algorithm. Namely, they turn out not only to improve the rate of convergence, but also to reduce the accumulated errors. From the mathematical perspective, this is due to the induced strong convexity of an appropriate potential function.

     

On equivalence of Floer's and quantum cohomology

We show that the Floer cohomology and quantum cohomology rings of the almost Kähler manifoldM, both defined over the Novikov ring of the loop space M, are isomorphic. We do it using a BRST trivial deformation of the topological A-model. The relevant aspect of noncompactness of the moduli of pseudoholomorphic instantons is discussed. It is shown nonperturbatively that any BRST trivial deformation of A model which does not change the dimensions of BRST cohomology does not change the topological correlation functions either.     

On the Discrete Hardy Inequality

Necessary and sufficient conditions for the boundedness of thediscrete Hardy operator of the form , from to when 0 < q < 1 <p , is given.