Electronic Current Density Induced by Uniform Magnetic Fields in Clarenes.

Some planar and non-planar clarenes have been studied using maps of magnetically induced quantum-mechanical current density and tools from differential topology to assess their magnetic response in connection with recent results by Du and Wang. Bond current strengths have been computed to estimate quantitative measures. Isosurfaces of the divergence of induced Lorentz force density have been shown to provide useful additional criteria, especially in the case of non-planar clarenes.

Chirality Sensing of Cryptochiral Guests with Prism[n]arenes.

Optical chirality sensing has gained significant attention in recent years. Within this field, the quest for stereodynamic chiroptical probes capable of detecting cryptochiral guests presents a formidable challenge. Macrocycles exhibiting planar chirality have emerged as promising candidates for amplifying the chirality of cryptochiral guests. In this study, we demonstrate that the formation of host-guest complexes between cryptochiral molecules and planar chiral prismarenes triggers electronic circular dichroism (ECD) signals via host-guest complexation-induced chirality amplification. The absolute configuration of the most stable chiral macrocyclic host-guest complex has been established by resorting to both exciton model and DFT computations. Furthermore, we demonstrated that this supramolecular chirality sensing system can be employed to determine the enantiomeric composition of scalemic mixtures by measuring the ECD bands intensity. The information described here opens the way for the use of prismarenes as stereodynamic probes for sensing of cryptochiral guests.

On the Unusual Global Aromaticity of Two Cyclopenta-ring-fused Oligo(m-phenylenes).

Some years ago, Jishan Wu reported the synthesis of 8MC and 10MC, two homologues of the cyclopenta-ring-fused oligo(m-phenylene) macrocycles mMC, each behaving as an annulene-within-an-annulene (AWA). This was a surprising result as the AWA behavior is rare. Both molecules have a partial polyradical character, enforced by the quest for restoring some aromatic character of benzene rings. However, that restoration brings back some coupling between the two annulenes. Indeed, we found that the geometry and the magnetically induced currents indicate that, while 8MC does have an AWA character, this is not the case of the larger 10MC. Limitations of the design strategy of AWA molecules should be taken into account in future attempts to prepare novel large coronenes.

Methylene-Bridged [6]-, [8]-, and [10]Cycloparaphenylenes: Size-Dependent Properties and Paratropic Belt Currents.

Cycloparaphenylenes (CPPs) and carbon nanobelts (CNBs) represent some of the most iconic cyclic molecular nanocarbons in recent chemistry owing to their unique properties derived from rigid, strained, and cyclic π-conjugated systems. In the last decade, the synthesis of various sizes of CPPs and CNBs has been achieved that allowed not only for investigating their size-dependent properties and strategically using such properties in various applications but also understanding the fundamental features of cyclic π-conjugated systems and molecular nanocarbons in general. Herein, we report on the synthesis, size-dependent properties, and paratropic belt currents of methylene-bridged [n]cycloparaphenylenes ([n]MCPP, n = 6, 8, 10). [8]MCPP and [10]MCPP were synthesized by the same strategy we developed for [6]MCPP synthesis. With readily available ethoxy-substituted pillar[8]arene and pillar[10]arene as precursors, [8]MCPP and [10]MCPP were successfully synthesized in three steps consisting of de-ethylation, triflation, and nickel-mediated aryl-aryl coupling. The structural and electronic properties of MCPPs were investigated by nuclear magnetic resonance analyses, absorption/fluorescence measurements, X-ray crystallographic analyses, and computational studies, revealing their interesting size-dependent properties. The differences in the size dependency between MCPPs and CPPs reflect the belt-form features of MCPPs, namely, methylene-bridging effects on MCPPs. Moreover, an interesting paratropic belt current along the MCPP backbone has been uncovered both experimentally and theoretically. The 1H NMR chemical shifts of MCPPs confirmed the presence of a paratropic belt current, whose strength rapidly decreases with increasing nanobelt size.

Electronic current densities and origin-independent property densities induced by optical fields.

The interaction of a molecule with optical fields is customarily interpreted by means of induced time-dependent electric polarizabilities, magnetizabilities and mixed electric-magnetic polarizabilities. In general, these properties can be rationalized by integrals of density functions formulated in terms of induced charge and current densities. In this perspective, we focus on what has been done so far at the theoretical level, and on what can be expected to be unveiled from the topological study of suitable density functions, endowed with the fundamental requirement of origin invariance. Densities characterized by such a property can be integrated all over the configuration space to obtain electric dipole polarizability and optical rotatory power. Corresponding maps visualize domains mainly involved in the molecular response. The diagonal components of origin-independent density tensor functions that, on integration, yield corresponding electric dipole polarizability tensor of benzene, naphthalene, phenanthrene and ovalene, have been computed, confirming the ubiquitous presence of counter-polarization regions in the proximity of the atomic nuclei. They are associated with toroidal electron currents, induced by time derivative of the electric field of impinging radiation. Electron (de)localization in these systems is readily observed and estimated. The optical rotation density of the carbonyl chromophore is studied in detail. Its essential feature is the separation in quadrants of alternating sign of density about the CO bond. The presence of an extrachromophoric perturbation determines asymmetry in the extension of the quadrant distribution, thus causing optical rotation.

On the JAP Method for the Indirect Determination of Delocalized Currents from Experimental Chemical Shifts.

The JAP model (after Jirásek, Anderson, and Peeks) to retrieve global current strengths from experimental 1 H chemical shifts has been tested with DFT computations. Both global and local tropicities are correctly predicted in most cases and the quantitative agreement is overall fair. An extension of the model is found to give improvement in an exemplary critical case, where the global delocalized current is negligible and the current density map is dominated by local currents.

Magnetic Characterization of the Infinitene Molecule.

The origin-independent current density induced by a perpendicular magnetic field in the infinitene molecule has been calculated, confirming the recently presented result by Orozco-Ic et al. ( Phys. Chem. Chem. Phys. 2022, 24, 6404-6409) of two disjointed global current pathways along the edges formed by 24 carbon atoms having the form of the infinity symbol. The current strength has been assessed along the C-C bonds forming the two separate circuits, whose particular shape provides a diamagnetic exaltation which is only 73% of the expected value for this aromatic molecule. Through space currents have been found along the bond paths determined by the electron density gradient, whose strength is 10% that of the aromatic benzene ring current. It is shown that the pair of high-field 1H NMR experimental signals carry the signature of the two global currents, which are counterrotating inside the fjord regions with respect to the rim of the coronene subunits.

Base-Promoted Cascade Reactions for the Synthesis of 3,3-Dialkylated Isoindolin-1-ones and 3-Methyleneisoindolin-1-ones.

Cascade reactions of ortho-carbonyl-substituted benzonitriles with ((chloromethyl)sulfonyl)benzenes as pronucleophiles led to new isoindolin-1-ones with a tetrasubstituted C-3 position or to (Z)-3-(sulfonyl-methylene)isoindolin-1-ones. The reactions start from readily available materials, are carried out under mild conditions, and do not require metal catalysis. Promoted only by the cheap and environmentally benign K2CO3 as the base, up to six elemental steps can be combined in a single pot. Hence, a sequential one-pot cascade/ß-elimination/alkylation furnished useful intermediates for the synthesis of aristolactam natural products. The observed selectivity and the mechanism were investigated by DFT studies.

Program Package for the Calculation of Origin-Independent Electron Current Density and Derived Magnetic Properties in Molecular Systems.

We present SYSMOIC, a program package for the calculation of the origin-independent current density induced at first order by an external magnetic field in planar and nonplanar molecular systems. Origin independence is obtained adopting the continuous transformation of the origin of the current density method, implemented at both density functional theory (DFT) and Hartree-Fock (HF) levels. Expansion coefficients for perturbed and unperturbed molecular orbitals, over basis sets containing up to m-type Gaussian functions, can be calculated by the package itself or obtained from a Gaussian calculation. A number of different functionalities presented so far in the literature that are connected to the induced current, such as current density maps for any orientation of the inducing magnetic field, net bond current strengths, stagnation graphs, magnetic shielding densities, vorticities, and anisotropies, are now made available all together in a single multiplatform package installation.

Assessment of the performance of DFT functionals in the fulfillment of off-diagonal hypervirial relationships.

Off-diagonal hypervirial relationships, combined with quantum mechanical sum rules of charge-current conservation, offer a way to test electronic excited-state transition energies and moments, which does not need any external reference. A number of fundamental relationships were recast into absolute deviations from zero, which have been used to assess the performance of some popular DFT functionals. Extended TD-DFT calculations have been carried out for a pool of molecules chosen for this purpose, adopting a large basis set to ensure high quality results. A partial agreement with previous benchmarks is observed.

Nonaromatic naphthocorroles.

New naphthocorrole ligands, display both the cavity size of corroles and the dianionic character of porphyrins. Nonaromatic and yet flaunting deceptively porphyrin-like optical spectra, they are readily accessible via a simple protocol.

Right- and left-handed PPI helices in cyclic dodecapeptoids.

Enantiomorphic right- and left-handed polyproline type I helices in four cyclic dodecapeptoids with methoxyethyl and propargyl side chains are observed for the first time by single crystal X-ray diffraction. The peculiar absence of NH⋯OC hydrogen bonds in peptoids unveils the role of intramolecular backbone-to-backbone CO⋯CO interactions and CH⋯OC hydrogen bonds in the stabilization of the macrocycle conformation. Moreover, intramolecular backbone-side chain C5 CH⋯OC hydrogen bonds emerge as a stabilizing factor.

Access to ß-Alkylated γ-Functionalized Ketones via Conjugate Additions to Arylideneisoxazol-5-ones and Mo(CO)6-Mediated Reductive Cascade Reactions.

1,4-Conjugate addition of ((chloromethyl)sulfonyl)benzenes to arylideneisoxazol-5-ones, followed by one-pot, N-selective trapping in the presence of electrophiles, was investigated. This strategy led to the synthesis of new, stable N-protected isoxazol-5-ones in good yields and high diastereolectivity. The study of the reactivity of obtained products in the presence of the Mo(CO)6/H2O system allowed the development of a cascade reaction leading to novel methyl ketones in high yields and unchanged dr bearing an uncommon chloromethinearylsulfonyl end group.

Disentangling the Contributions to the Proton Magnetic Shielding in Carbon Nanohoops and Nanobelts: Evidence for a Paratropic Belt-Current.

The proton NMR magnetic shieldings of the recently synthesized D3d isomers of methylene-bridged [6]cycloparaphenylene (MB[6]CPP) and [12]cyclophenacene hide in themselves the effect of a global paratropic current around the nanobelts, which is induced by a magnetic field parallel to the main symmetry axis of the molecules. The effect is particularly pronounced for the methylene protons of MB[6]CPP, especially for those facing inside the nanobelt. The small experimental chemical shift difference of only 0.2 ppm is incompatible with the separation of the signals caused by the belt curvature, which, by itself, is calculated to be larger than 1 ppm, with both signals shifted upfield with respect to the position detected for the nanobelt. A careful dissection of the proton magnetic shielding in terms of molecular orbital contributions, has permitted a quantitative assessment of the genuine effect on each different proton caused by a substantial paratropic belt-current, which brings all the signals in nice agreement with the experimental spectra.