From Macrocycles to Quantum Rings: Does Aromaticity Have a Size Limit?

ConspectusThe ring currents of aromatic and antiaromatic molecules are remarkable emergent phenomena. A ring current is a quantum-mechanical feature of the whole system, and its existence cannot be inferred from the properties of the individual components of the ring. Hückel's rule states that when an aromatic molecule with a circuit of [4n + 2] πelectrons is placed in a magnetic field, the field induces a ring current that creates a magnetic field opposing the external field inside the ring. In contrast, antiaromatic rings with 4n πelectrons exhibit ring currents in the opposite direction. This rule bears the name of Erich Hückel, and it grew from his molecular orbital theory, but modern formulations of Hückel's rule incorporate contributions from others, particularly William Doering and Ronald Breslow. It is often assumed that aromaticity is restricted to small molecular rings with up to about 22 πelectrons. This Account outlines the discovery of global ring currents in large macrocycles with circuits of up to 162 πelectrons. The largest aromatic rings yet investigated are cyclic porphyrin oligomers, which exhibit global ring currents after oxidation, reduction or optical excitation but not in the neutral ground state. The global aromaticity in these porphyrin nanorings leads to experimentally measurable aromatic stabilization energies in addition to magnetic effects that can be studied by NMR spectroscopy. Wheel-like templates can be bound inside these nanorings, providing excellent control over the molecular geometry and allowing the magnetic shielding to be probed inside the nanoring. The ring currents in these systems are well-reproduced by density functional theory (DFT), although the choice of DFT functional often turns out to be critical. Here we review recent contributions to this field and present a simple method for determining the ring current susceptibility (in nA/T) in any aromatic or antiaromatic ring from experimental NMR data by classical Biot-Savart calculations. We use this method to quantify the ring currents in a variety of aromatic rings. This survey confirms that Hückel's rule reliably predicts the direction of the ring current, and it reveals that the ring current susceptibility is surprisingly insensitive to the size of the ring. The investigation of aromaticity in even larger molecular rings is interesting because ring currents are also observed when mesoscopic metal rings are placed in a magnetic field at low temperatures. The striking similarity between the ring currents in molecules and mesoscopic metal rings arises because the effects have a common origin: a field-dependent phase shift in the electronic wave function. The main difference is that the magnetic flux through mesoscopic rings is much greater because of their larger areas, so their persistent currents are nonlinear and oscillatory with the applied field, whereas the flux through aromatic molecules is so small that their response is approximately linear in the applied field. We discuss how nonlinearity is expected to emerge in large molecular nanorings at high magnetic fields. The insights from this work are fundamentally important for understanding aromaticity and for bridging the gap between chemistry and mesoscopic physics, potentially leading to new functions in molecular electronics

Laser-Accelerated proton beams as diagnostics for cultural heritage

This paper introduces the first use of laser-generated proton beams as diagnostic for materials of interest in the domain of Cultural Heritage. Using laser-accelerated protons, as generated by interaction of a high-power short-pulse laser with a solid target, we can produce proton-induced X-ray emission spectroscopies (PIXE). By correctly tuning the proton flux on the sample, we are able to perform the PIXE in a single shot without provoking more damage to the sample than conventional methodologies. We verify this by experimentally irradiating materials of interest in the Cultural Heritage with laser-accelerated protons and measuring the PIXE emission. The morphological and chemical analysis of the sample before and after irradiation are compared in order to assess the damage provoked to the artifact. Montecarlo simulations confirm that the temperature in the sample stays safely below the melting point. Compared to conventional diagnostic methodologies, laser-driven PIXE has the advantage of being potentially quicker and more efficien

Watching bonds move in a large antiaromatic ring

In antiaromatic molecules, single and double bonds interconvert via a process called bond-shift valence tautomerization, which is often so fast that its rate is difficult to measure experimentally. In this issue of Chem, Wu and co-workers use dynamic NMR spectroscopy to study valence tautomerization in a giant antiaromatic macrocycle

From macrocycles to quantum rings: Does aromaticity have a size limit?

The ring currents of aromatic and antiaromatic molecules are remarkable emergent phenomena. A ring current is a quantum-mechanical feature of the whole system, and its existence cannot be inferred from the properties of the individual components of the ring. Hückel’s rule states that when an aromatic molecule with a circuit of [4n + 2] π electrons is placed in a magnetic field, the field induces a ring current that creates a magnetic field opposing the external field inside the ring. In contrast, antiaromatic rings with 4n π electrons exhibit ring currents in the opposite direction. This rule bears the name of Erich Hückel, and it grew from his molecular orbital theory, but modern formulations of Hückel’s rule incorporate contributions from others, particularly William Doering and Ronald Breslow. It is often assumed that aromaticity is restricted to small molecular rings with up to about 22 π electrons. This Account outlines the discovery of global ring currents in large macrocycles with circuits of up to 162 π electrons. The largest aromatic rings yet investigated are cyclic porphyrin oligomers, which exhibit global ring currents after oxidation, reduction or optical excitation but not in the neutral ground state. The global aromaticity in these porphyrin nanorings leads to experimentally measurable aromatic stabilization energies in addition to magnetic effects that can be studied by NMR spectroscopy. Wheel-like templates can be bound inside these nanorings, providing excellent control over the molecular geometry and allowing the magnetic shielding to be probed inside the nanoring. The ring currents in these systems are well-reproduced by density functional theory (DFT), although the choice of DFT functional often turns out to be critical. Here we review recent contributions to this field and present a simple method for determining the ring current susceptibility (in nA/T) in any aromatic or antiaromatic ring from experimental NMR data by classical Biot–Savart calculations. We use this method to quantify the ring currents in a variety of aromatic rings. This survey confirms that Hückel’s rule reliably predicts the direction of the ring current, and it reveals that the ring current susceptibility is surprisingly insensitive to the size of the ring. The investigation of aromaticity in even larger molecular rings is interesting because ring currents are also observed when mesoscopic metal rings are placed in a magnetic field at low temperatures. The striking similarity between the ring currents in molecules and mesoscopic metal rings arises because the effects have a common origin: a field-dependent phase shift in the electronic wave function. The main difference is that the magnetic flux through mesoscopic rings is much greater because of their larger areas, so their persistent currents are nonlinear and oscillatory with the applied field, whereas the flux through aromatic molecules is so small that their response is approximately linear in the applied field. We discuss how nonlinearity is expected to emerge in large molecular nanorings at high magnetic fields. The insights from this work are fundamentally important for understanding aromaticity and for bridging the gap between chemistry and mesoscopic physics, potentially leading to new functions in molecular electronics

Experimental and computational evaluation of the barrier to torsional rotation in a butadiyne-linked porphyrin dimer

The barrier to torsional rotation in a butadiyne-linked porphyrin dimer has been determined in solution using variable temperature UV-vis-NIR spectroscopy: ΔH = 5.27 ± 0.03 kJ mol−1, ΔS = 10.69 ± 0.14 J K−1 mol−1. The value of ΔH agrees well with theoretical predictions. Quantum chemical calculations (DFT) were used to predict the torsion angle dependence of the absorption spectrum, and to calculate the vibronic fine structure of the S0 → S1 absorption for the planar dimer, showing that the absorption band of the planar conformer has a vibronic component overlapping with the 〈0|0〉 absorption of the perpendicular conformer. The torsion barrier in the porphyrin dimer is higher than that of 1,4-diphenylbutadiyne (calculated ΔH = 1.1 kJ mol−1). Crystallographic bond lengths and IR vibrational frequencies confirm that there is a greater contribution of the cumulenic resonance form in butadiyne-linked porphyrin dimers than in 1,4-diphenylbutadiyne. The DFT frontier orbitals of the twisted conformer of the porphyrin dimer are helical, when calculated in the absence of symmetry. The helical character of these orbitals disappears when D2d symmetry is enforced in the 90° twisted conformer. Helical representations of the frontier orbitals can be generated by linear combinations of the more localised orbitals from a symmetry-constrained calculation but they do not indicate π-conjugation. This work provides insights into the relationship between electronic structure and conformation in alkyne-linked conjugated oligomers

Aromatic and antiaromatic ring currents in a molecular nanoring

Aromatic and antiaromatic molecules exhibit ring currents around their perimeters. Similar persistent currents are observed in metal rings, when the coherence length of the electrons is longer than the circumference of the ring. The relationship between these quantum mechanical phenomena is poorly understood, partly because they are studied in different size regimes: the largest aromatic molecules have diameters of about 1 nm, whereas persistent currents are found in rings with diameters of 20–1000 nm. It is not clear whether aromaticity and antiaromaticity are confined to small molecules, or whether the necessary quantum coherence can be achieved in large macrocycles. Here we show, using 1H NMR spectroscopy and density functional theory, that a six-porphyrin nanoring template complex c-P6·T6, with a diameter of 2.4 nm, is antiaromatic in its 4+ oxidation state and aromatic in its 6+ oxidation state. These species have circuits of 80 and 78 π electrons, respectively, and they are the largest aromatic and antiaromatic systems yet reported. The antiaromatic state has a huge paramagnetic susceptibility, despite having no unpaired electrons. This work demonstrates that a global ring current can be promoted in a macrocycle by adjusting its oxidation state to suppress the local ring currents of its components. The discovery of ring currents around a molecule with a circumference of 7.5 nm, at room temperature, shows that quantum coherence can persist in surprisingly large molecular frameworks, and implies that it will be possible to exploit quantum interference effects, such as Aharonov-Bohm oscillations, in molecular electronic devices

Experimental and computational evaluation of the barrier to torsional rotation in a butadiyne-linked porphyrin dimer

The barrier to torsional rotation in a butadiyne-linked porphyrin dimer has been determined in solution using variable temperature UV-vis-NIR spectroscopy: ΔH = 5.27 ± 0.03 kJ mol−1, ΔS = 10.69 ± 0.14 J K−1 mol−1. The value of ΔH agrees well with theoretical predictions. Quantum chemical calculations (DFT) were used to predict the torsion angle dependence of the absorption spectrum, and to calculate the vibronic fine structure of the S0 → S1 absorption for the planar dimer, showing that the absorption band of the planar conformer has a vibronic component overlapping with the 〈0|0〉 absorption of the perpendicular conformer. The torsion barrier in the porphyrin dimer is higher than that of 1,4-diphenylbutadiyne (calculated ΔH = 1.1 kJ mol−1). Crystallographic bond lengths and IR vibrational frequencies confirm that there is a greater contribution of the cumulenic resonance form in butadiyne-linked porphyrin dimers than in 1,4-diphenylbutadiyne. The DFT frontier orbitals of the twisted conformer of the porphyrin dimer are helical, when calculated in the absence of symmetry. The helical character of these orbitals disappears when D2d symmetry is enforced in the 90° twisted conformer. Helical representations of the frontier orbitals can be generated by linear combinations of the more localised orbitals from a symmetry-constrained calculation but they do not indicate π-conjugation. This work provides insights into the relationship between electronic structure and conformation in alkyne-linked conjugated oligomers

Global Aromaticity and Antiaromaticity in Porphyrin Nanoring Anions

Doping, through oxidation or reduction, is often used to modify the properties of π‐conjugated oligomers. In most cases, the resulting charge distribution is difficult to determine. If the oligomer is cyclic and doping establishes global aromaticity or antiaromaticity, then it is certain that the charge is fully delocalized over the entire perimeter of the ring. Here we show that reduction of a six‐porphyrin nanoring using decamethylcobaltocene results in global aromaticity (in the 6– state; [90 π]) and antiaromaticity (in the 4– state; [88 π]), consistent with Hückel’s rules. Aromaticity is assigned by NMR spectroscopy and density‐functional theory calculations

Global aromaticity and antiaromaticity in porphyrin nanoring anions

Doping, through oxidation or reduction, is often used to modify the properties of π‐conjugated oligomers. In most cases, the resulting charge distribution is difficult to determine. If the oligomer is cyclic and doping establishes global aromaticity or antiaromaticity, then it is certain that the charge is fully delocalized over the entire perimeter of the ring. Here we show that reduction of a six‐porphyrin nanoring using decamethylcobaltocene results in global aromaticity (in the 6– state; [90 π]) and antiaromaticity (in the 4– state; [88 π]), consistent with Hückel’s rules. Aromaticity is assigned by NMR spectroscopy and density‐functional theory calculations

Transient EPR Reveals Triplet State Delocalization in a Series of Cyclic and Linear π-Conjugated Porphyrin Oligomers

The photoexcited triplet states of a series of linear and cyclic butadiyne-linked porphyrin oligomers were investigated by transient Electron Paramagnetic Resonance (EPR) and Electron Nuclear DOuble Resonance (ENDOR). The spatial delocalization of the triplet state wave function in systems with different numbers of porphyrin units and different geometries was analyzed in terms of zero-field splitting parameters and proton hyperfine couplings. Even though no significant change in the zero-field splitting parameters (D and E) is observed for linear oligomers with two to six porphyrin units, the spin polarization of the transient EPR spectra is particularly sensitive to the number of porphyrin units, implying a change of the mechanism of intersystem crossing. Analysis of the proton hyperfine couplings in linear oligomers with more than two porphyrin units, in combination with density functional theory calculations, indicates that the spin density is localized mainly on two to three porphyrin units rather than being distributed evenly over the whole π-system. The sensitivity of the zero-field splitting parameters to changes in geometry was investigated by comparing free linear oligomers with oligomers bound to a hexapyridyl template. Significant changes in the zero-field splitting parameter D were observed, while the proton hyperfine couplings show no change in the extent of triplet state delocalization. The triplet state of the cyclic porphyrin hexamer has a much decreased zero-field splitting parameter D and much smaller proton hyperfine couplings with respect to the monomeric unit, indicating complete delocalization over six porphyrin units in this symmetric system. This surprising result provides the first evidence for extensive triplet state delocalization in an artificial supramolecular assembly of porphyrins