Spatial Magnetic Properties Research Articles

Identification of mesomeric substructures by through-space NMR shieldings (TSNMRS). Trimethine cyanine/merocyanine-like or aromatic π-electron delocalization?

The spatial magnetic properties, through-space NMR shieldings (TSNMRS), of amino-substituted heteroaromatic six-membered ring systems such as pyrylium/thiopyrylium analogues have been calculated using the GIAO perturbation method employing the nucleus independent chemical shift (NICS) concept and visualized as iso-chemical-shielding surfaces (ICSS) of various size and direction. The TSNMRS values were employed to quantify and visualize the existing aromaticity of the studied compounds. Due to strong conjugation of six-membered ring π-electrons and lone pairs of the exo-cyclic amino substituents (restricted rotation about partial C,N double bonds) the interplay of still aromatic and already dominating trimethine cyanine/merocyanine-like substructures can be estimated.

Y-aromaticity – existing: yes or no? An answer given on the magnetic criterion (TSNMRS)

The spatial magnetic properties (Through Space NMR Shieldings – TSNMRS) of a number of Y-shaped structures possessing 4n+2 π-electrons (i.a. the trimethylenemethane ions TMM2+, TMM2−, the guanidinium cation, substituted and hetero analogues) have been computed, visualized as Isochemical Shielding Surfaces (ICSS) of various size and direction, were examined subject to present Y-aromaticity and the results compared with energetic and geometric criteria obtained already.

Characterization and quantification of quasi-aromaticity by spatial magnetic properties (TSNMRS)

The spatial magnetic properties (Through Space NMR Shieldings—TSNMRS) of various types of structures with suggested quasi-aromaticity (a summaring topic: in detail push–pull, captodative, chelate, supramolecular aromaticity, etc.) have been computed, are visualized as Isochemical Shielding Surfaces (ICSS) of various size/direction and examined subject to identify and quantify present (partial) aromaticity. While the TSNMRS approach proves really helpful [even in cases of (4n+2) π-electron cyclic moieties formed via non-covalent polar interactions] quasi-aromaticity suggested for enol forms of 1,3-dicarbonyl compounds via resonance-assisted intramolecular and intermolecular hydrogen bonding cannot be confirmed.

Anisotropy effect of three-membered rings in (1)H NMR spectra: quantification by TSNMRS and assignment of the stereochemistry.

The spatial magnetic properties (through space NMR shieldings, TSNMRSs) of cyclopropane; of the heteroanalogous oxirane, thiirane, and aziridine; and of various substituted mono-, dis-, and tris-cyclic analogues have been computed by the GIAO perturbation method employing the nucleus independent chemical shift (NICS) concept and visualized as iso-chemical-shielding surfaces (ICSSs) of various size and direction. The TSNMRS values, thus obtained, can be employed to visualize the anisotropy (ring current) effect of the cyclopropane ring moiety. This approach has been employed to qualify and quantify substituent influences and contributions of appropriate ring heteroatoms O, NH, and S on the anisotropy (ring current) effect of three-membered ring moieties, and to assign the stereochemistry of mono-, bis-, and tris-cyclic structures containing cyclopropane as a structural element. Characteristic examples are included.

Are para-nitro-pyridine N-oxides quinonoid or benzenoid? An answer given by spatial NICS (TSNMRS)

The spatial magnetic properties (Through-Space NMR Shieldings—TSNMRS) of a number of substituted para-nitro-pyridine N-oxides have been computed, visualized as Iso–Chemical–Shielding–Surfaces (ICSS) of various size and direction, and were examined subject to the present quinonoid or benzenoid π-electron distribution of the six-membered ring.

Interplay of para- and diatropic ring currents [(anti)aromaticity] of macrocyclic rings subject to conformational influences, further annelation and hydrogenation of aromatic ring moieties

The spatial magnetic properties (Through Space NMR Shieldings—TSNMRS) of a variety of porphyrins, hemiporphyrazines and tetraoxo[8]circulenes have been computed, visualized as Iso-chemical Shielding Surfaces (ICSS) of various size and direction, and were examined subject to the interplay of present (para)-diatropic ring currents [(anti)aromaticity] and influences on the latter property originating from the macrocyclic ring conformation, further annelation and partial to complete hydrogenation of aromatic ring moieties. Caution seems to be indicated when concluding from a single NICS parameter to present (para)diatropic ring currents [(anti)aromaticity].

Accessing the Optical Magnetic Near-Field through Babinet’s Principle

Engineering the optical magnetic field with optical antennas or metamaterials extends the ways to control light-matter interaction. The slot antenna, as the electromagnetic dual of the linear rod antenna, provides the simplest form of a magnetic resonator tunable through its length. Using combined far- and near-field spectroscopy and imaging, and theory, we identify magnetic dipole and higher order bright and dark magnetic resonances at mid-infrared frequencies. From resonant length scaling and spatial near-field distribution, we confirm the applicability of Babinetʼs principle over the mid-infrared spectral region. Babinet's principle thus provides access to spatial and spectral magnetic field properties, leading to the targeted design of magnetic optical antennas.

Searching for Aromatic Chelate Rings. Oxygen versus Thio and Seleno Ligands

Abstract As a part of searching for fully aromatic chelate compounds, copper complexes of malondialdehyde as well as its sulfur and selenium derivatives were investigated using the DFT quantum chemical methods. Chelate complexes of both Cu(I) and Cu(II) ions wereconsidered. Aromaticity of the metal complexes studied were analyzed using NICS(0), NICS(1), PDI, Iring, MCI, KMCI and IB aromaticity indices, and by TSNMRS visualizations of the spatial magnetic properties. It seems that partial aromaticityof studied chelates increases when oxygen atoms in malondialdehyde are replaced by sulfur and selenium.

(Anti)aromaticity of dehydroannulenes of various ring size proved by the ring current effect in 1H NMR spectra

The spatial magnetic properties (Through-Space NMR Shieldings—TSNMRS) of already synthesized dehydro[n]annulenes of various ring size (from C12 to C20) have been computed, visualized as Isochemical Shielding Surfaces (ICSS) of various size and direction, and were examined subject to present (anti)aromaticity. For this purpose the thus quantified ring current effect of the macro cycles on proximate protons in proton NMR spectra was employed.

Antiaromaticity Proved by the Anisotropic Effect in 1H NMR Spectra

The spatial magnetic properties (through-space NMR shieldings, or TSNMRSs) of the antiaromatic 9-oxaanthracene anion 12(-) and of the corresponding 9-dimeric dianion 11(2-) have been calculated by the gauge-invariant atomic orbitals (GIAO) perturbation method employing the nucleus independent chemical shift (NICS) concept and visualized as iso-chemical-shielding surfaces (ICSSs) of various size and direction. The TSNMRS values, thus obtained, can be employed to indicate antiaromaticity by paratropic ring currents of the anionic compounds of 11(2-) and 12(-) studied and other neutral and ionic antiaromatic molecules from previous studies because anisotropic effects of functional groups in (1)H NMR spectra have quantitatively proven to be the molecular response property of theoretical spatial nucleus independent chemical shieldings (NICS).

Are lithium and sodium salts of N-(2-hydroxyphenyl)-salicylaldimine aromatic metalla-hetero[10]annulenes? An answer given by spatial magnetic properties (through space NMR shieldings—TSNMRS)

The spatial magnetic properties (through space NMR shieldings-TSNMRS) of the enol tautomer of N-(2-hydroxyphenyl)-salicylaldimine, the lithium and sodium salts in comparison with cyclodecapentaene and pyrano[2,3-b]pyrrole were studied to answer this question.

Spatial magnetic properties subject to lone pair and π electron delocalization in benzenoid and quinoid structures. Are quinoid tautomers really nonaromatic?

The spatial magnetic properties, through-space NMR shieldings (TSNMRS), of benzenoid and quinoid tautomeric structures such as benzodifurantrione and phenazine-type molecules have been calculated using the GIAO perturbation method employing the nucleus independent chemical shift (NICS) concept of Paul von Rague Schleyer and visualized as iso-chemical- shielding surfaces (ICSS) of various size and direction. The TSNMRS values were employed to quantify and visualize the partial aromaticity of the studied compounds. In the case of the surprisingly more stable quinoid tautomers, the aromaticity-synonymous with stability due to the conjugation of π electrons and lone pairs-was not found to be particularly reduced.

Chelatoaromaticity—existing: yes or no? An answer given by spatial magnetic properties (through space NMR shieldings—TSNMRS)

The spatial magnetic properties (through space NMR shieldings--TSNMRS) of metal complexes (with ligands such as acetylacetone, 3-hydroxy-pyran(4)one) and "metallobenzenes" have been calculated by the GIAO perturbation method and visualized as Iso-Chemical-Shielding Surfaces (ICSS) of various sizes and directions. The TSNMRS values, thus obtained, can be successfully employed to quantify and visualize partial aromaticity of the metallocyclic ring by comparison with the spatial magnetic properties of the corresponding non-complexed ligands in comparable structural and electronic situations, and benzene, respectively. Because anisotropy/ring current effects in (1)H NMR spectra proved to be the molecular response property of TSNMRS, the results obtained concerning partial "chelatoaromaticity" are experimentally ensured.

The anisotropic effect of functional groups in 1H NMR spectra is the molecular response property of spatial nucleus independent chemical shifts (NICS)—Conformational equilibria of exo/endotetrahydrodicyclopentadiene derivatives

The inversion of the flexible five-membered ring in tetrahydrodicyclopentadiene (TH-DCPD) derivatives remains fast on the NMR timescale even at 103 K. Since the intramolecular exchange process could not be sufficiently slowed for spectroscopic evaluation, the conformational equilibrium is thus inaccessible by dynamic NMR. Fortunately, the spatial magnetic properties of the aryl and carbonyl groups attached to the DCPD skeleton can be employed in order to evaluate the conformational state of the system. In this context, the anisotropic effects of the functional groups in the (1)H NMR spectra prove to be the molecular response property of spatial nucleus independent chemical shifts (NICS).

Subtle Trade-off Existing between (Anti)Aromaticity, Push−Pull Interaction, Keto−Enol Tautomerism, and Steric Hindrance When Defining the Electronic Properties of Conjugated Structures

The spatial magnetic properties (through space NMR shieldings, TSNMRS) of conjugated structures (benzenoid/quinonoid keto/enol tautomers, 1,3-dihydroxyaryl-2-aldehydes, Don-pi-Acc chromophores with trade-off existing push-pull vs aromatic behavior) have been calculated by the GIAO perturbation method employing the nucleus independent chemical shift (NICS) concept, and visualized as iso-chemical-shielding surfaces (ICSS) of various size and direction. The TSNMRS values, thus obtained, can be successfully employed to quantify and visualize (anti)aromaticity and to identify readily hereby zwitterionic structures due to push-pull behavior of the compounds studied. In addition, the push-pull behavior was quantified by the quotient (pi*/pi) approach of the central partial C=C double bond.

Identification of Benzenoid and Quinonoid Structures by Through-Space NMR Shieldings (TSNMRS)

The spatial magnetic properties (through-space NMR shieldings (TSNMRS)) of benzenoid and quinonoid structures (hydroquinone/p-benzoquinone, p-phenylendiamine/p-phenylendiimine, pentacene, and N-containing heteropentacenes) have been calculated by the GIAO perturbation method employing the nucleus-independent chemical shift (NICS) concept of Paul von Rague Schleyer and visualized as isochemical shielding surfaces (ICSS) of various size and direction. The TSNMRS values, thus obtained, can be successfully employed to quantify and visualize the (anti)aromaticity of the compounds studied and to identify readily the existence of benzenoid and quinonoid structures, respectively. As an alternative, computed (as compared with experimental) (1)H chemical shifts can be employed.

Visualization of homoaromaticity in cations, neutral molecules and anions by spatial magnetic properties (through space NMR shieldings)—an 1H/13C NMR chemical shift study

Prototypes for homoaromaticity in cations, neutral molecules, and anions are theoretically studied at the MP2 level of theory. For the global minimum structures on the potential energy surface both 1H/13C chemical shifts and spatial magnetic properties as through space NMR shieldings (TSNMRS) were calculated by the GIAO perturbation method. The TSNMRS are visualized as iso-chemical-shielding surfaces (ICSS) of different sign and size. Coincident experimental and computed 1H/13C chemical shifts afforded the possibility to decide from the TSNMRSs at hand on both the existence and the size of homoaromaticity in the molecules studied.

Quinoxalines XV. Convenient Synthesis and Structural Study of Pyrazolo[1,5-a]quinoxalines

A series of aryloxymethylquinoxaline oximes, hitherto unknown and synthesized from the corresponding aldehydes, afforded in only one step pyrazolo[1,5-a]quinoxalines in the presence of acetic anhydride at high temperatures. A formal [3,5]-sigmatropic rearrangement was proposed as the mechanistic rationale for this unprecedented transformation. Saponification with potassium hydroxide furnished the free phenol derivatives which were studied by NMR spectroscopy and accompanying theoretical DFT calculations, establishing intramolecular hydrogen bonding and the spatial magnetic properties. Additionally, mass spectrometric fragmentation was investigated by B/E-linked scans and collision-induced dissociation experiments. The fragmentation pattern devoted a new gas phase rearrangement process, which proved to be unique and characteristic for pyrazolo[1,5-a]quinoxalines.

Cyclobutadiene dianion derivatives – Planar 4c,6e or three-dimensional 6c,6e aromaticity?

The spatial magnetic properties (Through Space NMR Shieldings – TSNMRS) of two cyclobutadiene derivatives ( 2 and 5) and of a number of cyclobutadiene dianion derivatives ( 3, 4 and 6–8) have been calculated by the GIAO perturbation method employing the Nucleus-Independent Chemical Shift (NICS) concept of P. v. Ragué Schleyer, and visualized as Iso-Chemical-Shielding Surfaces (ICSS) of various size and direction. TSNMRS values can be successfully employed to quantify and visualize the (anti)aromaticity of the compounds studied and to discuss the influence of Li + complexation to cyclobutadiene dianion ( 4a, 7 and 8) on planar 4c,6e or three-dimensional 6c,6e aromaticity.