Interface Amorphization of Two-Dimensional Black Phosphorus upon Treatment with Diazonium Salts

Two-dimensional (2D) black phosphorus (BP) represents one of the most appealing 2D materials due to its electronic, optical, and chemical properties. Many strategies have been pursued to face its environmental instability, covalent functionalization being one of the most promising. However, the extremely low functionalization degrees and the limitations in proving the nature of the covalent functionalization still represent challenges in many of these sheet architectures reported to date. Here we shine light on the structural evolution of 2D-BP upon the addition of electrophilic diazonium salts. We demonstrated the absence of covalent functionalization in both the neutral and the reductive routes, observing in the latter case an unexpected interface conversion of BP to red phosphorus (RP), as characterized by Raman, ³¹P-MAS NMR, and X-ray photoelectron spectroscopies (XPS). Furthermore, thermogravimetric analysis coupled to gas chromatography and mass spectrometry (TG-GC-MS), as well as electron paramagnetic resonance (EPR) gave insights into the potential underlying radical mechanism, suggesting a Sandmeyer-like reaction.     

Strong Asymptotics of the Orthogonal Polynomials with Respect to a Measure Supported on the Plane

We consider the orthogonal polynomials with respect to the measure over the whole complex plane. We obtain the strong asymptotic of the orthogonal polynomials in the complex plane and the location of their zeros in a scaling limit where n grows to infinity with N . The asymptotics are described in terms of three (probability) measures associated with the problem. The first measure is the limit of the counting measure of zeros of the polynomials, which is captured by the g‐function much in the spirit of ordinary orthogonal polynomials on the real line. The second measure is the equilibrium measure that minimizes a certain logarithmic potential energy, supported on a region K of the complex plane. The third measure is the harmonic measure of K ^c with a pole at ∞ . This appears as the limit of the probability measure given (up to the normalization constant) by the squared modulus of the n^th orthogonal polynomial times the orthogonality measure, i.e., The compact region K that is the support of the second measure undergoes a topological transition under the variation of the parameter in a double scaling limit near the critical point given by we observe the Hastings‐McLeod solution to Painlevé II in the asymptotics of the orthogonal polynomials. © 2014 Wiley Periodicals, Inc.     

Isometric embeddings into Heisenberg groups

We study isometric embeddings of a Euclidean space or a Heisenberg group into a higher dimensional Heisenberg group, where both the source and target space are equipped with an arbitrary left-invariant homogeneous distance that is not necessarily sub-Riemannian. We show that if all infinite geodesics in the target are straight lines, then such an embedding must be a homogeneous homomorphism. We discuss a necessary and certain sufficient conditions for the target space to have this ‘geodesic linearity property’, and we provide various examples.     

Synthesis of (E)-2-(1-ferrocenylmethylidene)malonic acid derivatives by a cobalt-catalyzed domino reaction of ethyl diazoacetate, carbon monoxide and ferrocenylimines

The domino reaction of ethyl diazoacetate, carbon monoxide and ferrocenylimines was investigated in the presence of Co₂(CO)₈ as catalyst. In most cases the main products are 2-(1-ferrocenylmethylidene) malonates formed by an N(1)-C(4) cleavage of the primarily derived β-lactams. The latter compounds could only be isolated when the reaction was carried out at relatively low CO pressure, using an excess of ethyl diazoacetate. trans-N-(tert-Butyl)-3-ethoxycarbonyl-4-ferrocenyl-β-lactam proved to be the most stable one among these compounds and could be isolated in 55% yield. N-alkyl β-lactams were shown to undergo acidic cleavage leading to the E isomers of 2-(1-ferrocenylmethylidene) malonates as the main products. The structures of the two new compounds, (E)-2-ethoxycarbonyl-3-ferrocenyl-N-((R)-1-phenylethyl)-2-propenamide and trans-N-(tert-butyl)-3-ethoxycarbonyl-4-ferrocenyl-β-lactam were confirmed by X-ray crystallography. The relative thermodynamical stability of the products as well as the energetics of the acid-mediated cleavage of the β-lactam ring was elucidated with DFT calculations.     

Extractive separation,preconcentration, spectrophotometric and atomic absorption determination of gold as an ion associate with 2-[2-(4-methoxyphenylamino)vinyl]-1,3,3-trimethyl-3H-indolium chloride

Extractive separation, preconcentration, and determination of gold as an ion associate (IA) with 2-[2-(4-methoxyphenylamino)vinyl]-1,3,3-trimethyl-3H-indolium chloride in extracts by spectrophotometry and atomic absorption spectrometry were studied. The optimal conditions were found for the extraction of IA with aromatic hydrocarbons and acetate esters. The main chemical analytical properties of the ion associate were determined. The formation of IA enables extractive separation of gold from Al, Cr, Mn, Fe, Co, Ni, Zn, Cu, Cd, Pt, Hg, Bi, Ag, Pb, and Pd. By varying the volume ratio of the aqueous and organic phases in the range of (1–40): 1, one can combine extractive separation and the preconcentration of gold and decrease the detection limit for gold to 0.031 mg/L (extraction-spectrophotometric determination) or 0.084 μg/L (direct determination in extracts by electrothermal atomic absorption spectrometry). Procedures were developed for the determination of trace amounts of gold, and their performance characteristics were calculated.     

Enzyme-catalyzed kinetic resolution of N-Boc-trans-3-hydroxy-4-phenylpyrrolidine

The first enzyme-catalyzed kinetic resolution of tert-butyl-3-hydroxy-4-phenylpyrrolidine-1-carboxylate is presented. Enzyme, solvent and temperature optimization resulted in a new resolution method with E = 40 enantioselectivity. The acetate derivative of the (+)-(3S,4R) enantiomer formed while the (?)-(3R,4S) isomer remained intact. Very good enantioselectivities (E > 200) were achieved in the enzyme-catalyzed alcoholysis of the racemic acetate in i-propanol and t-butanol where the (+)-(3S,4R) enantiomer was prepared in pure form (ee > 99.7%). Absolute configuration of the (?)-(3R,4S)-enantiomer was determined by single crystal X-ray diffraction method.      

Enhancement of Ion Pairing of Sr(II) and Ba(II) Salts by a Tritopic Ion-Pair Receptor in Solution

Tritopic ion-pair receptors can bind bivalent salts in solution; yet, these salts have a tendency to form ion-pairs even in the absence of receptors. The extent to which such receptors can enhance ion pairing has however remained elusive. Here, we study ion pairing of M²⁺ (Ba²⁺, Sr²⁺) and X⁻ (I⁻, ClO₄⁻) in acetonitrile with and without a dichlorooxacalix[2]arene[2]triazine-related receptor containing a pentaethylene-glycol moiety. We find marked ion association already in receptor-free solutions. When present, most of the MX⁺ ion-pairs are bound to the receptor and the overall degree of ion association is enhanced due to coordinative, hydrogen-bonding, and anion-π interactions. The receptor shows higher selectivity for iodides but also stabilizes perchlorates, despite the latter are often considered as weakly coordinating anions. Our results show that ion-pair binding is strongly correlated to ion pairing in these solutions, thereby highlighting the importance of taking ion association in organic solvents into account.