Aromaticity Reversal in the Lowest Excited Triplet State of Archetypical Möbius Heteroannulenic Systems

The aromaticity reversal in the lowest triplet state (T₁) of a comparable set of Hückel/Möbius aromatic metalated expanded porphyrins was explored by optical spectroscopy and quantum calculations. In the absorption spectra, the T₁ states of the Möbius aromatic species showed broad, weak, and ill‐defined spectral features with small extinction coefficients, which is in line with typical antiaromatic expanded porphyrins. In combination with quantum calculations, these results indicate that the Möbius aromatic nature of the S₀ state is reversed to Möbius antiaromaticity in the T₁ state. This is the first experimental observation of aromaticity reversal in the T₁ state of Möbius aromatic molecules.     

Viability of Möbius Topologies in [26]‐ and [28]Hexaphyrins

Recently, hexaphyrins have emerged as a promising class of π‐conjugated molecules that display a range of interesting electronic, optical, and conformational properties, including the formation of stable Möbius aromatic systems. Besides the Möbius topology, hexaphyrins can adopt a variety of conformations with Hückel and twisted Hückel topologies, which can be interconverted under certain conditions. To determine the optimum conditions for viable Möbius topologies, the conformational preferences of [26]‐ and [28]hexaphyrins and the dynamic interconversion between the Möbius and Hückel topologies were investigated by density functional calculations. In the absence of meso substituents, [26]hexaphyrin prefers a planar dumbbell conformation, strongly aromatic and relatively strain free. The Möbius topology is highly improbable: the most stable tautomer is 33 kcal mol^?1 higher in energy than the global minimum. On the other hand, the Möbius conformer of [28]hexaphyrin is only 6.5 kcal mol^?1 higher in energy than the most stable dumbbell conformation. This marked difference is due to aromatic stabilization in the Möbius 4n electron macrocycle as opposed to antiaromatic destabilization in the 4n+2 electron system, as revealed by several energetic, magnetic, structural, and reactivity indices of aromaticity. For [28]hexaphyrins, the computed activation barrier for interconversion between the Möbius aromatic and Hückel antiaromatic conformers ranges from 7.2 to 10.2 kcal mol^?1, in very good agreement with the available experimental data. The conformation of the hexaphyrin macrocycle is strongly dependent on oxidation state and solvent, and this feature creates a promising platform for the development of molecular switches.     

PdII Complexes of [44]‐ and [46]Decaphyrins: The Largest Hückel Aromatic and Antiaromatic,and Möbius Aromatic Macrocycles

Reductive metalation of [44]decaphyrin with [Pd₂(dba)₃] provided a Hückel aromatic [46]decaphyrin Pd^II complex, which was readily oxidized upon treatment with DDQ to produce a Hückel antiaromatic [44]decaphyrin Pd^II complex. In CH₂Cl₂ solution the latter complex underwent slow tautomerization to a Möbius aromatic [44]decaphyrin Pd^II complex which exists as a mixture of conformers in dynamic equilibrium. To the best of our knowledge, these three Pd^II complexes represent the largest Hückel aromatic, Hückel antiaromatic, and Möbius aromatic complexes to date.     

PdII Complexes of [44]‐ and [46]Decaphyrins: The Largest Hückel Aromatic and Antiaromatic,and Möbius Aromatic Macrocycles

Reductive metalation of [44]decaphyrin with [Pd₂(dba)₃] provided a Hückel aromatic [46]decaphyrin Pd^II complex, which was readily oxidized upon treatment with DDQ to produce a Hückel antiaromatic [44]decaphyrin Pd^II complex. In CH₂Cl₂ solution the latter complex underwent slow tautomerization to a Möbius aromatic [44]decaphyrin Pd^II complex which exists as a mixture of conformers in dynamic equilibrium. To the best of our knowledge, these three Pd^II complexes represent the largest Hückel aromatic, Hückel antiaromatic, and Möbius aromatic complexes to date.     

A Doubly Zwitterionic Antiaromatic [28]Hexaphyrin Formed upon Deprotonation of 5,20‐Di(N‐methyl‐4‐pyridinium)‐Substituted [28]Hexaphyrin

A rectangular 5,20‐di(4‐pyridyl) [26]hexaphyrin was reduced with NaBH₄ to give the corresponding twisted Möbius aromatic [28]hexaphyrin. Subsequent double N‐methylation gave a dicationic 5,20‐di(N‐methyl‐4‐pyridinium) [28]hexaphyrin, which was converted to a doubly zwitterionic and Hückel antiaromatic [28]hexaphyrin upon deprotonation with sodium methoxide.     

A Möbius Aromatic [28]Hexaphyrin Bearing a Diethylamine Group: A Rigid but Smooth Conjugation Circuit

The reaction of [26]hexaphyrin with triethylamine in the presence of BF₃?OEt₂ and O₂ furnished a diastereomeric mixture of a diethylamine‐bearing [28]hexaphyrin as a rare example of a Möbius aromatic metal‐free expanded porphyrin. The Möbius aromaticity of these molecules is large, as indicated by their large diatropic ring currents, which are even preserved at 100 °C, owing to their internally multiply bridged robust structure with a smooth conjugation network. These molecules were reduced with NaBH₄ to give an antiaromatic [28]hexaphyrin, and were oxidized with MnO₂ to give aromatic [26]hexaphyrins, both through a Möbius‐to‐Hückel topology switch induced by a C? N bond cleavage.     

ESI‐MS/MS of expanded porphyrins: a look into their structure and aromaticity

Electrospray mass spectrometry/mass spectrometry was used to investigate the gas‐phase properties of protonated expanded porphyrins, in order to correlate those with their structure and conformation. We have selected five expanded meso‐pentafluorophenyl porphyrins, respectively, a pair of oxidized/reduced fused pentaphyrins (22 and 24 π electrons), a pair of oxidized/reduced regular hexaphyrins (26 and 28 π electrons) and a regular doubly N‐fused hexaphyrin (28 π electrons). The gas‐phase behavior of the protonated species of oxidized and reduced expanded porphyrins is different. The oxidized species (aromatic Hückel systems) fragment more extensively, mainly by the loss of two HF molecules. The reduced species (Möbius aromatic or Möbius‐like aromatic systems) fragment less than their oxidized counterparts because of their increased flexibility. The protonated regular doubly fused hexaphyrin (non‐aromatic Hückel system) shows the least fragmentation even at higher collision energies. In general, cyclization through losses of HF molecules decreases from the aromatic Hückel systems to Möbius aromatic or Möbius‐like aromatic systems to non‐aromatic Hückel systems and is related to an increase in conformational distortion. Copyright © 2016 John Wiley & Sons, Ltd.     

An Unusually Small Singlet–Triplet Gap in a Quinoidal 1,6‐Methano[10]annulene Resulting from Baird’s 4n π‐Electron Triplet Stabilization

Within the continuum of π‐extended quinoidal electronic structures exist molecules that by design can support open‐shell diradical structures. The prevailing molecular design criteria for such structures involve proaromatic nature that evolves aromaticity in open‐shell diradical resonance structures. A new diradical species built upon a quinoidal methano[10]annulene unit is synthesized and spectroscopically evaluated. The requisite intersystem crossing in the open‐shell structure is accompanied by structural reorganization from a contorted Möbius aromatic‐like shape in S₀ to a more planar shape in the Hückel aromatic‐like T₁. This stability was attributed to Baird’s Rule which dictates the aromaticity of 4n π‐electron triplet excited states.     

Mechanochemically Triggered Topology Changes in Expanded Porphyrins

A hitherto unexplored class of molecules for molecular force probe applications are expanded porphyrins. This work proves that mechanical force is an effective stimulus to trigger the interconversion between Hückel and Möbius topologies in [28]hexaphyrin, making these expanded porphyrins suitable to act as conformational mechanophores operating at mild (sub-1 nN ) force conditions. A straightforward approach based on distance matrices is proposed for the selection of pulling scenarios that promote either the planar Hückel topology or the three lowest lying Möbius topologies. This approach is supported by quantum mechanochemical calculations. Force distribution analyses reveal that [28]hexaphyrin selectively allocates the external mechanical energy to molecular regions that trigger Hückel–Möbius interconversions, explaining why certain pulling scenarios favor the Hückel two-sided topology and others favor Möbius single-sided topologies. The meso-substitution pattern on [28]hexaphyrin determines whether the energy difference between the different topologies can be overcome by mechanical activation.     

Retaining Hückel Aromaticity in the Triplet Excited State of Azobenzene

The implication of the potential concept of aromaticity in the relaxed lowest triplet state of azobenzene, an efficient molecular switch, using elementary aromaticity indices based on magnetic, electronic, and geometric criteria has been discussed. Azobenzene exhibits a major Hückel aromatic character retained in the diradical lowest relaxed triplet state (T₁) by virtue of a twisted geometry with partial delocalization of unpaired electrons in the perpendicular p-orbitals of two nitrogen atoms to the corresponding phenyl rings. The computational analysis has been expanded further to stilbene and N-diphenylmethanimine for an extensive understanding of the effect of closed-shell Hückel aromaticity in double-bond-linked phenyl rings. Our analysis concluded that stilbene has Hückel aromatic character in the relaxed T₁ state and N-diphenylmethanimine has a considerable Hückel aromaticity in the phenyl ring near the carbon atom while a paramount Baird aromaticity in the phenyl ring near the nitrogen atom of the C=N double bond. The results reveal the application of excited-state aromaticity as a general tool for the design of molecular switches.     

Interplay of Hückel and Möbius Aromaticity in Metal-Metal Quintuple Bonded Complexes of Cr,Mo, and W with Amidinate Ligand: Ab initio DFT and Multireference Analysis**

The aromaticity of metal-metal quintuple bonded complexes of the type M₂L₂ (M=Cr, Mo, and W; L=amidinate) are studied employing gauge including magnetically induced ring current (GIMIC) analysis and electron density of delocalized bonds (EDDB). It is found that the complexes possess two types of aromaticity: i) Hückel aromaticity through delocalization of ligand π electrons with metal-metal δ-bond-forming 6 conjugated electrons (4π and 2δ) ring; ii) Craig-Möbius aromaticity through delocalization of π electrons of both the ligands with metal d-orbitals in Craig type orientation forming 10π electrons ring with a double twist. Extended transition state natural orbital chemical valence (ETS-NOCV) and canonical molecular orbital natural chemical shielding (CMO-NCS) analysis confirm the Craig-Möbius type arrangement of the orbitals. Furthermore, the unprecedented Hückel and Möbius type aromaticity is confirmed from the plot of the current pathways using 3D line integral convolution (3D-LIC) plots. The metal-metal bond order also increases down the group as justified from the complete active space self-consistent field (CASSCF) analysis. Due to an increase in the π and δ electron conjugation, both the Hückel and Möbius aromaticity increase down the group.     

A Fully Conjugated Porphyrin-[36]Octaphyrin-Porphyrin Hybrid Tape Exhibiting Möbius Aromaticity

Directly meso-meso linked porphyrin-tetrabromo[36]octaphyrin-porphyrin hybrid trimer 10 was successfully synthesized via acid-catalyzed condensation reaction and subsequent oxidation. Zn^II-metalation of 10 induced transannular meso-meso bond formation to give Möbius aromatic bis-Zn^II octaphyrin 11 , which was oxidized by DDQ/Sc(OTf)₃ to provide fully conjugated porphyrin-[36]octaphyrin-porphyrin hybrid tape 12 as the first example of porphyrin tape exhibiting Möbius aromaticity. Hybrid tape 12 displays significantly red-shifted absorption and small electrochemical HOMO-LUMO gap, indicating the effective conjugation through the whole chromophores.     

Doubly N‐Fused [24]Pentaphyrin Silicon Complex and Its Fluorosilicate: Enhanced Möbius Aromaticity in the Fluorosilicate

Treatment of nonaromatic N‐fused [24]pentaphyrin with trichloromethylsilane in the presence of a base afforded doubly N‐fused [24]pentaphyrin and its silicon complex. Addition of fluoride ion to the silicon complex led to the formation of its fluorosilicate as an unprecedented monoanionic six‐coordinated Si^IV complex of porphyrinoid. Treatment of the fluorosilicate with acid led to the recovery of the silicon complex. The doubly N‐fused pentaphyrin, the silicon complex, and the fluorosilicate were all characterized as distinct Möbius aromatic molecules by spectroscopic measurements and X‐ray crystallographic analyses. Importantly, the second N‐fusion reaction, Si‐incorporation and fluoride addition to the Si‐atom enhanced the aromaticity of doubly N‐fused [24]pentaphyrins in this order. Tamao–Fleming oxidation of the silicon complex gave β‐keto doubly N‐fused pentaphyrin and triply fused [24]pentaphyrin, which were nonaromatic and Hückel anti‐aromatic, respectively.     

Figure‐eight Octaphyrin Bis‐Ge(IV) Complexes: Synthesis,Structures, Aromaticity,and Chiroptical Properties

Highly twisted structures of expanded porphyrin provide a prominent basis to unravel the relationship between aromaticity and chirality. Here we report the synthesis of bis‐Ge(IV) complexes of [38]octaphyrin that display rigid figure‐eight structures. Two bis‐Ge(IV) [38]octaphyrin isomers with respect to the stereochemistry of the axial hydroxy groups on the germanium ions were obtained and found to be aromatic. Upon oxidation with MnO₂, these [38]octaphyrin complexes were converted to a single syn‐type isomer of [36]octaphyrin with retained figure‐eight conformation. The enantiomers have been successfully separated by HPLC equipped with a chiral stationary phase. While aromatic [38]octaphyrin Ge(IV) complexes showed quite large molar circular dichroism of up to Δ?=1500 M^?1cm^?1 with a dissymmetry factor g_abs of 0.035, weakly antiaromatic [36]octaphyrin Ge(IV) complexes underscored moderate values; Δ?=540 M^?1cm^?1 with g_abs of 0.023. Thus, the figure‐eight octaphyrin scaffold has been proved to be an attractive platform for novel chiroptical materials with tunable aromaticity.     

Hückel and Möbius Expanded para‐Benziporphyrins: Synthesis and Aromaticity Switching

The four expanded p‐benziporphyrins A,C‐di‐p‐benzi[24]pentaphyrin(1.1.1.1.1), N‐fused A‐p‐benzi[24]pentaphyrin, A,D ‐di‐p‐benzi[28]hexaphyrin(1.1.1.1.1.1), and A,C‐di‐p‐benzi[28]hexaphyrin(1.1.1.1.1.1) were obtained in three‐component Lindsey‐type macrocyclizations. These compounds were explored as macrocyclic ligands and as potential aromaticity switches. A BODIPY‐like difluoroboron complex was obtained from the A,C‐di‐p‐benzi[24]pentaphyrin, whereas A,C‐di‐p‐benzi[28]hexaphyrin yielded a Möbius‐aromatic Pd^II complex containing fused pyrrole and phenylene subunits. Conformational behavior, tautomerism, and acid‐base chemistry of the new macrocycles were characterized by means of NMR spectroscopy and DFT calculations. Free base N‐fused A‐p‐benzi[24]pentaphyrin showed temperature‐dependent Hückel–Möbius aromaticity switching, whereas the A,C‐di‐p‐benzi[28]hexaphyrin formed a Möbius‐aromatic dication.     

Topology Switching in [32]Heptaphyrins Controlled by Solvent,Protonation, and meso Substituents

The switching of topology between “figure‐eight”, Möbius, and untwisted conformations in [32]heptaphyrins(1.1.1.1.1.1.1) has been investigated by using density functional theory calculations. Such a change is achieved by variation of one internal dihedral angle and, if properly controlled, can provide access to molecular switches with unique optical and magnetic properties. In this work, we have explored different conformational control methods, such as solvent, protonation and meso substituents. Despite its antiaromatic character, most of the [32]heptaphyrins (R=H, CH₃, CF₃, Ph, C₆F₅) adopt a figure‐eight conformation in the neutral state, owing to their more‐effective hydrogen‐bonding interactions. The aromatic Möbius topology is only preferred with dichlorophenyl groups, which minimize the steric hindrance that arises from the bulky chlorine atoms. The conformational equilibrium is sensitive to the solvent, so polar solvents, such as DMSO, further stabilize the Möbius conformation. Protonation induces a conformational change into the Möbius topology, irrespective of the meso‐aryl groups. In the triprotonated species, the conformational switch is blocked and a non‐twisted conformer becomes much more stable than the figure‐eight conformation. We have shown that the relative energies of the protonated [32]heptaphyrins are dominated by aromaticity. Importantly, this topology switching induces a dramatic change in the magnetic properties and reactivity of the macrocycles, as revealed by several energetic, magnetic, structural, and reactivity indices of aromaticity.     

Disclosure of Ground-State Zimmerman-Möbius Aromaticity in the Radical Anion of [6]Helicene and Evidence for 4π Periodic Aromatic Ring Currents in a Molecular “Metallic” Möbius Strip

In 1966, Zimmerman proposed a type of Möbius aromaticity that involves through-space electron delocalization; it has since been widely applied to explain reactivity in pericyclic reactions, but is considered to be limited to transition-state structures. Although the easily accessible hexahelicene radical anion has been known for more than half a century, it was overlooked that it exhibits a ground-state minimum and robust Zimmerman-Möbius aromaticity in its central noose-like opening, becoming, hence, the oldest existing Möbius aromatic system and with smallest Möbius cycle known. Despite its overall aromatic stabilization energy of 13.6 kcal mol⁻¹ (at B3LYP/6-311+G**), the radical also features a strong, globally induced paramagnetic ring current along its outer edge. Exclusive global paramagnetic currents can also be found in other fully delocalized radical anions of 4N+2 π-electron aromatic polycyclic benzenoid hydrocarbons (PAH), thus questioning the established magnetic criterion of antiaromaticity. As an example of a PAH with nontrivial topology, we studied a novel Möbius[16]cyclacene that has a non-orientable surface manifold and a stable closed-shell singlet ground state at several density functional theory levels. Its metallic monoanion radical (0.0095 eV band gap at HSE06/6-31G* level) is also wave-function stable and displays an unusual 4π-periodic, magnetically induced ring current (reminiscent of the transformation behaviour of spinors under spatial rotation), thus indicating the existence of a new, Hückel-rule-evading type of aromaticity.     

Bond-alternating Hückel-Möbius and related,twisted linear,cyclic and helical systems—their molecular orbitals,energies and phase correlation upon dissociation

Cyclic group formalism and screw symmetry operation are used to clarify and generalize the definition of Hückel and Möbius systems. It is shown that the Möbius ring system has half-integral pseudo-angular momentum similar to that of spin space, and that applications of Möbius electronics to chemical reactions have been based on truncated single-circle Möbius rings which have unique beginning and end (Sect. 2). This concept is illustrated by application to the [1, 7] antarafacial hydrogen shift (Appendix A and Figs. A1–A3). Definition of a Hüickel versus Möbius ring system for in-plane and out-of-plane π, δ and φ orbitals as well as the appropriate relative angle of twists are given (Sect. 2 and Table 1). Using the concept of the compatibility of the twist (screw) angle and rotation around a ring, we also derive the proper phase coherence and energy correlation between a parent cyclic (Hückel or Möbius) molecule and its dissociated linear fragments (Sect. 4). The concept of parentage in diabatic fragmentation is discussed. Forfinite, open, helical chain molecules, an exact periodic boundary condition based on the compatibility of twist angle and number of turns in a helical ring parent molecule is applied to derive their analytic wave functions (Sect. 5 and Table 2). Forbond-alternating “linear” and cyclic Hückel and Möbius systems we also derive the explicit LCAO-MO wavefunctions, energies, their degeneracies and their exact corresponding quantum members for even and odd atom systems at highest bonding and lowest antibonding levels (Sect. 3, Figs. 1–3). The corresponding wavefunctions and energies for uniform-bond systems are given for comparison and for completeness (Sect. 3).     

Viability of möbius topologies in [26]- and [28]hexaphyrins

Recently, hexaphyrins have emerged as a promising class of π-conjugated molecules that display a range of interesting electronic, optical, and conformational properties, including the formation of stable M?bius aromatic systems. Besides the M?bius topology, hexaphyrins can adopt a variety of conformations with Hückel and twisted Hückel topologies, which can be interconverted under certain conditions. To determine the optimum conditions for viable M?bius topologies, the conformational preferences of [26]- and [28]hexaphyrins and the dynamic interconversion between the M?bius and Hückel topologies were investigated by density functional calculations. In the absence of meso?substituents, [26]hexaphyrin prefers a planar dumbbell conformation, strongly aromatic and relatively strain free. The M?bius topology is highly improbable: the most stable tautomer is 33?kcal?mol(-1) higher in energy than the global minimum. On the other hand, the M?bius conformer of [28]hexaphyrin is only 6.5?kcal?mol(-1) higher in energy than the most stable dumbbell conformation. This marked difference is due to aromatic stabilization in the M?bius 4n electron macrocycle as opposed to antiaromatic destabilization in the 4n+2 electron system, as revealed by several energetic, magnetic, structural, and reactivity indices of aromaticity. For [28]hexaphyrins, the computed activation barrier for interconversion between the M?bius aromatic and Hückel antiaromatic conformers ranges from 7.2 to 10.2?kcal?mol(-1) , in very good agreement with the available experimental data. The conformation of the hexaphyrin macrocycle is strongly dependent on oxidation state and solvent, and this feature creates a promising platform for the development of molecular switches.