Accepting a commission to review progress in the subject embodied in our title is, perhaps, to take up something of a ‘poisoned chalice’. One of us, contributing on this same topic more than 20 years ago at the 1979 International Symposium on Aromaticity in Dubrovnik, wrote1 “A cynic would say that there are actually only two difficulties in discussing the subject of ‘aromaticity’ and ‘ring currents’sdeciding what is meant by ‘ring current’, and assigning a meaning to the term ‘aromaticity’!” That comment, though ostensibly facetious, had serious intent: it did encapsulate, with only a modicum of exaggeration, the problems that inherently beset any assessment such as the one attempted at Dubrovnik1 and in the present review. At the heart of the matter lies the undeniable fact that neither ring currents nor aromaticity are physical observables. Nevertheless, the intervening period has seen the ring-current idea, at least, become generally less controversial and more accepted than it once was. At the time of our opening quotation, one of us and Haigh had just published an exhaustive review2 of the ring-current concept covering the period up to about 1980sthe end of what might now be regarded as the era of semiempirical calculations in this field.2 This review2 (1979/1980) concluded that “the ‘ring current’ picture has proved itself ... to have great power in rationalising, at least qualitatively, the magnetic properties of π-electron systems. It is so pictorial that one can almost feel what is happening when a [conjugated] molecule is subjected to a magnetic field. Whatever advances the future may bring, it may be that the favourite habitat of the ‘ring current’ will be that in which it was born and brought up, namely, that of semi-empirical π-electron theory”. In other words, these authors were sanguine that, at the time (ca. 1980), the ring-current idea was gently coming to the end of its natural, useful life. However, as recently as 1997, when reviewing progress concerning the status of the ring-current model during the decade and a half or so after 1980s a period in this field that we have dubbed3 ‘the ab initio era’sthe present authors3 were initially somewhat surprised to find themselves concluding that “the ‘ring-current’ idea has well survived the first 15 years of the ab initio era.” Lazzeretti’s subsequent magnum opus4 on ring currents has more than confirmed this. By contrast, the sheer fact that in 2001sthe very first year of the 21st centurysthe American Chemical Society has seen fit to run this particular issue of Chemical Reviews shows that the concept of Aromaticity is as elusive as it ever was (see section II). There are three reasons for our not feeling obliged or inclined to present, in this review, an exhaustive, systematic, or historical critique of the ring-current concept itself. First, as we have just claimed, the idea of a ring current seems more secure now than it was 20 years ago, and it would appear that less apology or justification is needed for invoking it. Second, we ourselves have, in any case, only recently updated 1349 Chem. Rev. 2001, 101, 1349−1383

https://www.fc.up.pt/pessoas/jfgomes/documentos/ArtigosPDF/ChemRev,%20101,%201349-83(2001).pdf

Aromaticity and ring currents.

FT-IR characterization of the surface acidity of different titanium dioxide anatase preparations

Publisher Summary This chapter focuses on organic catalysis over crystalline alumiosilicates. Zeolites are crystalline aluminosilicates composed of SiO4 and AlO4 tetrahedra arranged in various geometric patterns. The chapter discusses reactions over a wide variety of crystalline aluminosilicates and emphasizes on catalysis over X- and Y-type faujasites. Unusual opportunities for organic catalysis were found to exist when these were base exchanged to substantially eliminate their alkali metal content. It is shown that catalytic activity in ion-exchanged faujasites is influenced by cation type, cation location in the lattice, zeolite Si/Al ratio, and the presence of proton donors. The existence of several crystallographically distinct cation locations provides the basis for a potential heterogeneity of sites in catalytic reactions. The Linde workers made calculations for the electrostatic field strengths of surface cations near SII and SIII in an X-type zeolite of Si/Al ratio 1.0 and in a Y-type zeolite of Si/Al ratio 2.0. In both cases, the fields has been significantly larger near SIII than SII at a distance of 2 Ǻ from the center of the cation for the univalent cation-exchanged systems, provided both sites are occupied.

Organic Catalysis over Crystalline Aluminosilicates

Various isomeric structures of the hydrated clusters of sulfuric acid, H2SO4(H2O)n (n = 1−5), are examined using a density functional molecular orbital method. Due to the small energy difference between trans and cis conformations about two OH groups of sulfuric acid, there are three types of isomeric forms of the hydrated clusters of sulfuric acid which involve the proton nontransferred trans conformer, the proton transferred trans conformer, and the proton nontransferred cis conformer of sulfuric acid. In the case of transoid H2SO4, the proton transferred ion-pair structures become more stable than the proton nontransferred structures as the number of water molecules increases. The hydrated clusters of the cis conformation remain neutral hydrogen-bonded structures even if the number of water molecules increases. All stable clusters tend to form multi-cyclic structures. While both protons of sulfuric acid participate in cyclic hydrogen bonding in the neutral structures, the OH group of HSO4- in the ion-p...

Coexistence of Neutral and Ion-Pair Clusters of Hydrated Sulfuric Acid H2SO4(H2O)n (n = 1−5)A Molecular Orbital Study

Vibrational Sum Frequency Spectroscopy Studies of the Influence of Solutes and Phospholipids at Vapor/Water Interfaces Relevant to Biological and Environmental Systems

Vibrational sum frequency spectroscopy studies of the influence of solutes and phospholipids at vapor/water interfaces relevant to biological and environmental systems.

Infrared Spectra of Methane-, Fluoro-, and Chlorosulfonic Acids

: The infrared absorption spectra in the range 4000 to 400/cm of the vapors above liquid H2SO4, 1:1 H2-SO4 D2SO4, and D2SO4 were measured and assigned to the respective gaseous molecules as well as equilibrium concentrations of SO3. SO2 was observed as a decomposition product. Assignment of the frequencies to the normal modes was made using correlations with the related near-tetrahedral molecules X-SO2-Y and with spectra of the condensed phases. Some frequencies are predicted for H2CrO4 and for unassociated gaseous chlorosulfonic acid. (Author)

Scaria M. Chackalackal

Papers

Infrared Spectra of Methane-, Fluoro-, and Chlorosulfonic Acids

Infrared spectra of the vapors above sulfuric and deuteriosulfuric acids

Infrared Spectra of Difluorophosphoric Acid1