A comparative study of the dimers of selected hydroxybenzenes

Hydroxybenzenes are the parent compounds of large classes of derivatives, many of which exhibit biological activities. This work presents the results of a comparative study of the dimers of selected hydroxybenzenes, considering all the possible mutual geometrical arrangements of the two monomers and comparing their relative stabilities and interaction energies. The OH···OH hydrogen bond between the two monomers is the dominant stabilizing factor, with frequent preference for mutual perpendicularity of the two aromatic rings. C? H···O unconventional H‐bonds, OH···π unconventional H‐bonds, H···π interactions and π··π interactions also may play significant roles. The factors stabilizing individual hydroxybenzenes (presence of intramolecular hydrogen bonds; number, positioning and orientation of the OH groups; symmetry features) have greater influence on the dimers' relative energy than on the interaction energy between monomers. While results from different calculations methods (HF, MP2, and DFT/B3LYP) show consistency for all the features just‐mentioned, they show some relevant differences in the way they take into account different types of interactions between monomers, resulting in some differences in the geometry arrangements of the monomers in the lowest energy dimers and in differences in the relative preferences among higher‐energy dimer geometries. © 2011 Wiley Periodicals, Inc. Int J Quantum Chem, 2012     

Is Electrostatics Sufficient to Describe Hydrogen‐Bonding Interactions?

The stability and geometry of a hydrogen‐bonded dimer is traditionally attributed mainly to the central moiety A?H???B, and is often discussed only in terms of electrostatic interactions. The influence of substituents and of interactions other than electrostatic ones on the stability and geometry of hydrogen‐bonded complexes has seldom been addressed. An analysis of the interaction energy in the water dimer and several alcohol dimers—performed in the present work by using symmetry‐adapted perturbation theory—shows that the size and shape of substituents strongly influence the stabilization of hydrogen‐bonded complexes. The larger and bulkier the substituents are, the more important the attractive dispersion interaction is, which eventually becomes of the same magnitude as the total stabilization energy. Electrostatics alone are a poor predictor of the hydrogen‐bond stability trends in the sequence of dimers investigated, and in fact, dispersion interactions predict these trends better.     

Supramolecular Luminescent Lanthanide Dimers for Fluoride Sequestering and Sensing

Lanthanide complexes (Ln=Eu, Tb, and Yb) that are based on a C₂‐symmetric cyclen scaffold were prepared and characterized. The addition of fluoride anions to aqueous solutions of the complexes resulted in the formation of dinuclear supramolecular compounds in which the anion is confined into the cavity that is formed by the two complexes. The supramolecular assembly process was monitored by UV/Vis absorption, luminescence, and NMR spectroscopy and high‐resolution mass spectrometry. The X‐ray crystal structure of the europium dimer revealed that the architecture of the scaffold is stabilized by synergistic effects of the Eu? F? Eu bridging motive, π stacking interactions, and a four‐component hydrogen‐bonding network, which control the assembly of the two [EuL] entities around the fluoride ion. The strong association in water allowed for the luminescence sensing of fluoride down to a detection limit of 24 nM .     

Mass spectrometry detection of minor new meridianins from the antarctic colonial ascidians Aplidium falklandicum and Aplidium meridianum

Taking into account the broad biological activities found in the meridianin indole alkaloids isolated to date, we have re‐examined the organic extracts of an Antarctic collection of the tunicates Aplidium meridianum and A. falklandicum (Chordata: Ascidiacea) by HPLC in conjunction with a high‐resolution mass spectrometer (HPLC‐MS). A new set of analogs of meridianins A–G has been detected, and their structures are proposed on the basis of the molecular formulae identified by LC‐HRMS analysis using a C18 column with a gradient of water/acetonitrile and an LTQ‐FT‐MS Orbitrap detector. Remarkably, dimers derived from meridianin A and from meridianin B or E were also detected. Our findings provide further evidence of the broad variability within the meridianin‐like derivatives of this highly bioactive alkaloid family. Copyright © 2015 John Wiley & Sons, Ltd.     

Ion tree‐based structure elucidation of acetophenone dimers (AtA) from Acronychia pedunculata and their identification in extracts by liquid chromatography electrospray ionization LTQ‐Orbitrap mass spectrometry

Acronychia‐type acetophenones (AtA) is a chemical group of compounds of important structural and biological interest, abundant in Acronychia species. However, there are no data available for their characterization using mass spectrometry. In the current work, AtA have been investigated by multistage high resolution mass spectrometry and both electrospray ionization and atmospheric pressure chemical ionization, in positive and negative mode, were utilized for their structure elucidation and identification. The analysis of AtA using a linear ion trap‐Orbitrap analyzer enabled the structural determination of key fragment ions and cleavages, which can be used for the structural characterization thereof. A systematic nomenclature based on protonated and deprotonated fragment ions under collision‐induced dissociation conditions and decision trees for the structural determination of AtA are proposed. Furthermore, taking advantage of the characteristic fragmentation patterns, a selective Ultra High Performance Liquid Chromatography Electrospray Ionization multistage Mass Spectrometry (UHPLC‐ESI(‐)‐MSⁿ) method was developed and successfully applied for the dereplication of known AtA and the identification of potentially new ones in Acronychia extracts. Despite the structure similarity and the presence of isomers, accurate characterization of known and unknown AtA derivatives was possible. Copyright © 2015 John Wiley & Sons, Ltd.     

Solution or Gas Phase? Oxidation and Radical Formation in Electrospray Ionization Mass Spectrometry (ESI MS)

The relationship between one‐electron (e^?) oxidation processes and the formation of radical cations of endogenous and exogenous compounds in vivo is of considerable interest. This paper reports on the experiments that allow FTICR mass spectrometric (MS) detection of ion signals that are consistent with the formation of radical cations of caffeine (CA) and theophylline (TP) during electrospray ionization (ESI) in ESI FTICR MS and in on‐line electrochemistry (EC)/ESI FTICR MS in positive mode. Significantly, the signals of the radicals of CA^?+ and TP^?+can be enhanced by simple modifications of the operating conditions in ESI MS, facilitating investigations of radical formation and related reactions.     

Structures and thermodynamic properties of aluminum oxyhalides: a computational study

The molecular geometries and vibrational frequencies of aluminum oxyhalides, AlOX, and their dimers, (AlOX)₂, have been calculated by MP2 and density functional methods. The monomeric molecules are linear while the dimers have a D _2h -symmetry geometry with a four-membered ring, in which the oxygen atoms serve as bridging ligands. Different thermodynamic properties have been calculated; for AlOBr and AlOI for the first time.     

Conformational Dynamics of Monomer‐ versus Dimer‐like Features in a Naphthalenediimide‐Based Conjugated Cyclophane

The design and synthesis of an enantiomeric pair of 1,8‐diethynylanthracene‐bridged naphthalenediimide (NDI)‐based cyclophanes ( Cyclo‐NDI s) are reported. Each enantiomer of Cyclo‐NDI exhibits a circularly polarized luminescence signal with a relatively large luminescence dissymmetry factor (g_lum=±8×10^?3). We have further investigated the modulation of through‐space electronic communication between co‐facially oriented NDIs in a discrete Cyclo‐NDI with changes in the temperature. Tuning of the electronic communication results from the conformational transformation of monomer‐ versus dimer‐like features of Cyclo‐NDI , as confirmed by UV/Vis, fluorescence, circular dichroic, and NMR spectroscopic analysis. The temperature‐dependent optical response in the Cyclo‐NDI through the conformational transformation could be utilized as a highly sensitive and reversible optical thermometer in a wide temperature range (100 to ?80 °C).     

Rational Development of Remote C−H Functionalization of Biphenyl: Experimental and Computational Studies

A simple and efficient nitrile‐directed meta‐C?H olefination, acetoxylation, and iodination of biaryl compounds is reported. Compared to the previous approach of installing a complex U‐shaped template to achieve a molecular U‐turn and assemble the large‐sized cyclophane transition state for the remote C?H activation, a synthetically useful phenyl nitrile functional group could also direct remote meta‐C?H activation. This reaction provides a useful method for the modification of biaryl compounds because the nitrile group can be readily converted to amines, acids, amides, or other heterocycles. Notably, the remote meta‐selectivity of biphenylnitriles could not be expected from previous results with a macrocyclophane nitrile template. DFT computational studies show that a ligand‐containing Pd–Ag heterodimeric transition state (TS) favors the desired remote meta‐selectivity. Control experiments demonstrate the directing effect of the nitrile group and exclude the possibility of non‐directed meta‐C?H activation. Substituted 2‐pyridone ligands were found to be key in assisting the cleavage of the meta‐C?H bond in the concerted metalation–deprotonation (CMD) process.