The influence of ms-substitution on the properties of 3,3′-bis(dipyrrolylmethenes) and their coordination compounds

We have compared the coordination properties of decamethyl-substituted 3,3′-bis-(dipyrrolylmethenes) (H₂L) with different ms-spacers separating the dipyrrolylmethene domains: methylene -CH₂-, methoxyphenylmethylene -CH(p-C₆H₄OMe)-, and trifluoromethylmethylene -CH(CF₃)-. The stable binuclear homoligand complexes [M₂L₂] are formed in reactions of the ligands with Co(II), Ni(II), Cu(II), Zn(II), Cd(II), and Hg(II) acetates. In the cases of all H₂L ligands the thermodynamic constants of the complex formation reactions increase in the following series: Cu(II) < Cd(II) < Hg(II) < Ni(II) < Co(II) < Zn(II). The change in -CH₂- ms-spacer to -CH(p-C₆H₄OMe)- or -CH(CF₃)- results in a decrease in the constant of H₂L complex formation by 1–4 orders of magnitude, the cation being the same. The influence of ms-substitution on the stability and luminescence properties of [M₂L₂] has been discussed.     

Preparation and spectral properties of Zn(II) complexes with aryl-substituted dipyrrolylmethene and azadipyrrolylmethene

The homoleptic complexes of Zn(II) with 3,3′,5,5‘-tetraphenyl-2,2’-dipyrrolylmethene and 3,3′,5,5′-tetraphenyl-ms-aza-2,2′-dipyrrolylmethene [ZnL₂] have been prepared, and their spectral and luminescent properties have been studied. The complex with 3,3′,5,5′-tetraphenyl-2,2′-dipyrrolylmethene exhibited an intense fluorescence in the nonpolar medium, efficiently quenched in the polar solvents; thus, it can be used as a fluorescent sensor of the medium polarity.     

Synthesis,stability in solutions,and spectral and thermal properties of alkyl-substituted 3,3′-bis(dipyrromethene) hydrobromides

3,3′-Bis(dipyrromethene) dihydrobromides (H₂L · 2HBr) with various types of alkylation have been synthesized. On the basis of IR, ¹H NMR, and electronic absorption spectra, spectrophotometric titration, and thermogravimetry, conclusions have been drawn about the influence of structural factors on the optical and thermal properties and salt stability in solutions. An increase in the degree of alkylation causes a significant high-frequency shift of the N-H stretching vibration band in the IR spectra, an upfield shift of the ¹H NMR signals of NH protons, a decrease in the auxochromic effects of protons on the aromatic system of the chromophore, and an increase in the salt stability in solutions in the presence of nucleophilic reagents and in the thermal stability in air and argon.     

Synthesis and photochemical properties of 3,6-di-<Emphasis Type="Italic">tert</Emphasis>-butyl-9<Emphasis Type="Italic">H</Emphasis>-carbazole derivatives

Method of synthesis has been developed for a series of 3,6-di-tert-butyl-9H-carbazole derivatives and their photochemical properties have been investigated. The dependence of the Steglich esterification reaction on the nature of the catalyst was studied. The synthesized compounds show fluorescent emission in the range 400–600 nm with a high quantum yield.     

Synthesis,spectral-luminescent properties of B(III) and Zn(II) complexes with alkyl- and aryl-substituted dipyrrins and azadipyrrins

Effect of complexing atom, molecular structure of dipyrrolylmethene and its aza analog on spectral-luminescent properties of heteroleptic boron(III) and homoleptic zinc(II) complexes with 3,3′,5,5′-tetramethyl-2,2′-dipyrrolylmethene, 3,3′,5,5′-tetraphenyl-2,2′-dipyrrolylmethene, and 3,3′,5,5′-tetraphenyl-ms-aza-2,2′-dipyrrolylmethene in organic solvent solutions was studied. The complexes were found to exhibit strong chromophore (λ = 350–690 nm, ? ～ 10⁵ L/mol cm) and fluorescent properties. Quantum yield (γ^fl) for fluoroborate complexes reaches 100% and is weakly dependent on medium nature. The value of γ^fl for phenyl- and alkyl-substituted zinc(II) dipyrrolylmethenates in nonpolar solvents is not higher 0.3 and 0.03, respectively; complete fluorescence quenching is observed in electron-donating solvents. Aza-substitution at the meso spacer causes considerable shift of electronic absorption and fluorescence spectra to the red region but completely quenches fluorescence of zinc(II) chelates and decreases γ^fl of boron(III) complex to 0.04.     

Tandem queueing system with infinite and finite intermediate buffers and generalized phase-type service time distribution

A tandem queueing system with infinite and finite intermediate buffers, heterogeneous customers and generalized phase-type service time distribution at the second stage is investigated. The first stage of the tandem has a finite number of servers without buffer. The second stage consists of an infinite and a finite buffers and a finite number of servers. The arrival flow of customers is described by a Marked Markovian arrival process. Type 1 customers arrive to the first stage while type 2 customers arrive to the second stage directly. The service time at the first stage has an exponential distribution. The service times of type 1 and type 2 customers at the second stage have a phase-type distribution with different parameters. During a waiting period in the intermediate buffer, type 1 customers can be impatient and leave the system. The ergodicity condition and the steady-state distribution of the system states are analyzed. Some key performance measures are calculated. The Laplace–Stieltjes transform of the sojourn time distribution of type 2 customers is derived. Numerical examples are presented.     

The High Sensitive and Selective “Off-On” Fluorescent Zn2+ Sensor Based on the Bis(2,4,7,8,9-pentamethyldipyrrolylmethene-3-yl)methane

A fluorescent chemosensor based on the 3,3′-bis(dipyrrin) bearing two chromophoric dipyrrin units was synthesized, which showed a strongly enhanced fluorescent intensity in the presence of Zn²⁺ ions and a high selectivity toward Zn²⁺ ions over a wide range of tested metal ions in organic solvents.     

Complexation between decamethyl-3,3′-bis(dipyrrolylmethene) and zinc(II), copper(II), and cobalt(II) acetates

Decamethyl-3,3′-bis(dipyrrolylmethene) dihydrobromide H₂L · 2HBr (H₂L is bis(3,4,7,8,9-pentamethylpyrrol-3-yl)methane), which is the simplest representative of a novel class of oligo(dipyrrolylmethenes) belonging to chromophore chelating nonmacrocyclic ligands, were examined by ¹H NMR, IR, and electronic absorption spectroscopy. Complexation reactions of H₂L · 2HBr with M(AcO)₂ (M = Zn(II), Cu(II), and Co(II)) in DMF at 298.15 K were monitored by electronic absorption spectroscopy and studied by the molar ratio method. The thermodynamic constants K ⁰ of these reactions were estimated. The d metal ions coordinate H₂L to give the binuclear homoleptic complexes [M₂L₂]. The reactions proceed through the intermediate binuclear heteroleptic complex [M₂L(AcO)₂] detected by spectroscopic methods. The thermodynamic stabilities of [M₂L₂] and [M₂L(AcO)₂] increase when moving from Cu(II) to Zn(II) and Co(II). The probability of formation and stability of [M₂L₂] containing 3,3′-bis(dipyrrolylmethene) are substantially higher than those of analogous complexes with the 2,2′-isomer (decamethyl-2,2′-biladienea, c). The low K ⁰ values for the complexation between H₂L and Cu(AcO)₂ are due to slow oxidation of the biladiene ligand into a bilatriene with participation of Cu²⁺ ions.     

Immobile Indices and CQ-Free Optimality Criteria for Linear Copositive Programming Problems

Set-Valued and Variational Analysis - We consider problems of linear copositive programming where feasible sets consist of vectors for which the quadratic forms induced by the corresponding linear...