Molecular, supramolecular structure and catalytic activity of transition metal complexes of phenoxy acetic acid derivatives

Six mononuclear complexes [M(L₁)₂(H₂O)₄] (M = Co(II), 1a and M = Mn(II), 1b), [Cu(L₁)₂(H₂O)₂] (1c), [Cu(L₁)₂(H₂O)(Py)₂] (1d), [Cu(L₃)(H₂O)Cl] · H₂O (3a) and [Co(Sal)(H₂O)(Py)₃] · 2ClO₄ · H₂O (3b) of phenoxyacetic acid derivatives and Schiff base were determined by single crystal X-ray diffraction. The Co(II) (1a) and Mn(II) (1b) complexes are isomorphous. X-ray crystal structural analyses reveal that these coordination complexes form polymeric structure via formation of different types of hydrogen bonding and π-stacking interactions in solid. Thermal analysis along with the powder X-ray diffraction data of these complexes shows the importance of the coordinated and/or crystal water molecules in stabilizing the MOF structure. Complexes 1a, 1c, 3a show marginal catalytic activity in the oxidation of olefins to epoxides in the presence of i-butyraldehyde and molecular oxygen.     

Acyclic diaminocarbene-based Thiele,Chichibabin, and Müller hydrocarbons

Thiele, Chichibabin and Müller hydrocarbons are considered as classical Kekulé diradicaloids. Herein we report the synthesis and characterization of acyclic diaminocarbene (ADC)-based Thiele, Chichibabin, and Müller hydrocarbons. The calculated singlet–triplet energy gaps are ΔE_S–T = −27.96, −3.70, −0.37 kcal mol⁻¹, respectively, and gradually decrease with the increasing length of the π-conjugated spacer (p-phenylene vs. p,p′-biphenylene vs. p,p′′-terphenylene) between the two ADC-scaffolds. In agreement with the calculations, we also experimentally observed the enhancement of paramagnetic diradical character as a function of the length of the π-conjugated spacer. ADC-based Thiele''s hydrocarbon is EPR silent and exhibits very well resolved NMR spectra, whereas ADC-based Müller''s hydrocarbon displays EPR signals and featureless NMR spectra at room temperature. The spacer also has a strong influence on the UV-Vis-NIR spectra of these compounds. Considering that our methodology is modular, these results provide a convenient platform for the synthesis of an electronically modified new class of carbon-centered Kekulé diradicaloids.

We report the synthesis of acyclic diaminocarbene (ADC)-scaffold based Thiele, Chichibabin, and Müller hydrocarbons. Studies support that the singlet-triplet energy gap depends on the π-conjugated spacer between the ADC scaffolds.     

Structure of hydrated clusters of tetrahydroisoquinoline [THIQ-(H2O)(n=1,3)] investigated by jet spectroscopy

The hydrated clusters of tetrahydroisoquinoline have been investigated by laser-induced fluorescence (LIF), UV-UV hole burning, and IR-UV double-resonance spectroscopy in a seeded supersonic jet. Clusters of different sizes and isomeric structures have different 0-0 transitions (origins) in the LIF spectrum. UV-UV hole burning spectroscopy has been used to identify different cluster species and their vibrational modes. The structures of the clusters have been predicted by comparing the observed OH and NH frequencies in the IR-UV double-resonance spectra with the results calculated at different levels of sophistication. It is found that the water molecules form linear and six- and eight-membered cyclic H-bonded structures at the nitrogen center of 1:1, 1:2, and 1:3 clusters, respectively.     

Buyer-supplier currency exchange rate flexibility contracts in global supply chains

This paper analyzes a decentralized global supply chain under a newsvendor setting, where a supplier delivers a certain quantity of a single product to a buyer in accordance with the terms of a mutually agreed upon contract. This contract is signed prior to the delivery of the product and subsequent payment, thus, exposing the supply chain to the risk of currency exchange rate fluctuations. We propose two types of currency exchange rate flexibility contracts to explore the characteristics of exchange rate risk mitigation policies for the buyer and the supplier. Furthermore, we investigate the effects of the contract structures on the optimal order quantity, as well as the expected profits of both supply chain members. Our results show that the optimal order quantity of the buyer decreases when the wholesale price is uncertain due to exchange rate volatility. Also, both our proposed contracts tend to improve the expected profits of both the buyer and the supplier, when the payment is made in the supplier’s currency, indicating the desirability of adopting such contractual agreements from the perspective of both parties. On the other hand, when the payment is made in the buyer’s currency, our suggested contracts do not yield such win-win scenarios. Finally, we examine the effectiveness of availing the services of a local vendor, which is capable of satisfying any demand in excess of the quantity ordered from the foreign source with short notice, in order to mitigate the risks associated with an overseas order.     

Placing a finite size facility with a center objective on a rectangular plane with barriers

This paper addresses the finite size 1-center placement problem on a rectangular plane in the presence of barriers. Barriers are regions in which both facility location and travel through are prohibited. The feasible region for facility placement is subdivided into cells along the lines of Larson and Sadiq [R.C. Larson, G. Sadiq, Facility locations with the Manhattan metric in the presence of barriers to travel, Operations Research 31 (4) (1983) 652–669]. To overcome complications induced by the center (minimax) objective, we analyze the resultant cells based on the cell corners. We study the problem when the facility orientation is known a priori. We obtain domination results when the facility is fully contained inside 1, 2 and 3-cornered cells. For full containment in a 4-cornered cell, we formulate the problem as a linear program. However, when the facility intersects gridlines, analytical representation of the distance functions becomes challenging. We study the difficulties of this case and formulate our problem as a linear or nonlinear program, depending on whether the feasible region is convex or nonconvex. An analysis of the solution complexity is presented along with an illustrative numerical example.     

An efficient phosphate sensor: tripodal quinoline excimer transduction

A novel quinoline based tripodal receptor that shows intermolecular excimer emission has been designed and synthesized. The excimer emission has been used to confirm the selective recognition of phosphate ion. It combines three different types of N-donor with the elegant fluorescent signaling properties.     

Growth and microstructure for visible emission and surface optical phonon mode of Zn–ZnO nanostructure

The Zn–ZnO nanostructured thin films were prepared in carbon matrix using a cost-effective vacuum-carbon arc method. On increasing graphitization with ZnO, the grazing incidence X-ray diffraction pattern showed that the intensity of the ZnO peak increases, whereas that of the Zn peak decreases. X-ray line profile analysis and transmission electron microscopy were employed to investigate the microstructural evolution of Zn–ZnO nanostructure during vacuum arc processing. A growth mechanism is proposed for the Zn–ZnO nanostructure when reaction with carbon-containing gas inside the reactor wall takes place. Detailed studies of photoluminescence bands clearly exhibit the intensity variation of violet and blue-green bands on increasing graphitization ratio. Using the dielectric continuum approach, surface optical phonon modes of the Zn–ZnO nanostructure were studied for different synthesized samples.     

A novel biflavonyloxymethane from Pongamia pinnata and its radical quenching activity

The root bark of Pongamia pinnata Pierre (syn P. glabra Vent.) has afforded a new biflavonyloxymethane, pongabiflavone, along with a known furanoflavone, 3-methoxy-(7, 8, 2", 3") furanoflavone. The structure of this new compound was elucidated from extensive spectral studies, including 2D-NMR spectroscopic experiments. The antioxidant, radical quenching activity- superoxide and nitric oxide quenching activities of both pongabiflavone and previously isolated karanjabiflavone have been evaluated which can be a key to cure Psoriasis.     

Seven-coordinate anion complex with a tren-based urea: binding discrepancy of hydrogen sulfate in solid and solution states

Structural characterization of a hydrogen sulfate complex with a tren-based urea suggests that the anion is coordinated with six NH···O bonds (d(N···O) = 2.857 (3) to 3.092 (3) ?) and one OH···O bond (d(O···O) = 2.57 (2) ?) from three receptors; however, in solution the anion is bound within the pseudo-cavity of one receptor.