Shape-Assisted Self-Assembly of Hexa-Substituted Carpyridines into 1D Supramolecular Polymers.

The extent of the influence that molecular curvature plays on the self-assembly of supramolecular polymers remains an open question in the field. We began addressing this fundamental question with the introduction of "carpyridines", which are saddle-shaped monomers that can associate with one another through π-π interactions and in which the rotational and translational movements are restricted. The topography displayed by the monomers led, previously, to the assembly of highly ordered 2D materials even in the absence of strong directional interactions such as hydrogen bonding. Here, we introduce a simple strategy to gain control over the dimensionality of the formed structures yielding classical unidimensional polymers. These have been characterized using well-established protocols allowing us to determine and confirm the self-assembly mechanism of both fibers and sheets. The calculated interaction energies are significantly higher than expected for flexible self-assembling units lacking classical "strong" non-covalent interactions. The versatility of this supramolecular unit to assemble into either supramolecular fibers or 2D sheets with strong association energies highlights remarkably well the potential and importance of molecular shape for the design of supramolecular materials and the applications thereof.

The impact of spin-orbit coupling on fine-structure and spin polarisation in photoexcited porphyrin triplet states.

The photoexcited triplet states of porphyrins show great promise for applications in the fields of opto-electronics, photonics, molecular wires, and spintronics. The magnetic properties of porphyrin triplet states are most conveniently studied by time-resolved continuous wave and pulse electron spin resonance (ESR). This family of techniques is singularly able to probe small yet essential details of triplet states: zero-field splittings, g-anisotropy, spin polarisation, and hyperfine interactions. These characteristics are linked to spin-orbit coupling (SOC) which is known to have a strong influence on photophysical properties such as intersystem crossing rates. The present study explores SOC effects induced by the presence of Pd2+ in various porphyrin architectures. In particular, the impact of this relativistic interaction on triplet state fine-structure and spin polarisation is investigated. These properties are probed using time-resolved ESR complemented by electron-nuclear double resonance. The findings of this study could influence the future design of molecular spintronic devices. The Pd2+ ion may be incorporated into porphyrin molecular wires as a way of controlling spin polarisation.

Saddles as rotational locks within shape-assisted self-assembled nanosheets.

Two-dimensional (2D) materials are a key target for many applications in the modern day. Self-assembly is one approach that can bring us closer to this goal, which usually relies upon strong, directional interactions instead of covalent bonds. Control over less directional forces is more challenging and usually does not result in as well-defined materials. Explicitly incorporating topography into the design as a guiding effect to enhance the interacting forces can help to form highly ordered structures. Herein, we show the process of shape-assisted self-assembly to be consistent across a range of derivatives that highlights the restriction of rotational motion and is verified using a diverse combination of solid state analyses. A molecular curvature governed angle distribution nurtures monomers into loose columns that then arrange to form 2D structures with long-range order observed in both crystalline and soft materials. These features strengthen the idea that shape becomes an important design principle leading towards precise molecular self-assembly and the inception of new materials.

Azatriseptanes: Strained Framework Analogs of [7,7,7]Circulenes.

Invited for the cover of this issue is the group of Michel Rickhaus at the University of Zurich. The image depicts the "unearthing" of the highly contorted azatriseptane, a carbon framework consisting of three fused seven-membered rings surrounding a central nitrogen. Read the full text of the article at 10.1002/chem.202203954.

Azatriseptanes: Strained Framework Analogs of [7,7,7]Circulenes.

The synthesis and characterization of heptagon-embedded polycyclic aromatic compounds are essential for understanding the effect of negative curvature on carbon allotropes such as fullerenes and graphenes that have applications in functional organic materials. However, owing to the synthetic difficulties in functionalizing and embedding seven-membered rings, these strain-challenged structures are relatively unexplored. We report here the synthesis, characterization, and properties of a triarylamine core bridged with ethano chains at the 2,2'-positions. In doing so, we provide access to the first heterocycle containing three fused heptagon rings with a nitrogen at its core (BATA-NHAc). X-ray crystallographic analysis and DFT calculations revealed a remarkably strained structure wherein two of the bridged aryl units approach coplanarity, while the third ring is twisted out of plane at 70°. UV-vis and emission spectroscopies identify red-shifted absorption and concentration-dependent emission profiles, respectively, as a result of the unique conformation and self-assembly properties of BATA-NHAc. Furthermore, cyclic voltammetry shows a decrease in the oxidation potential for BATA-NHAc in comparison to the non-bridged analog. This study opens new avenues in understanding the structure-property relationships of curved π-aromatics and the construction of π-frameworks of increasing complexity.

Shape-assisted self-assembly.

Self-assembly and molecular recognition are critical processes both in life and material sciences. They usually depend on strong, directional non-covalent interactions to gain specificity and to make long-range organization possible. Most supramolecular constructs are also at least partially governed by topography, whose role is hard to disentangle. This makes it nearly impossible to discern the potential of shape and motion in the creation of complexity. Here, we demonstrate that long-range order in supramolecular constructs can be assisted by the topography of the individual units even in the absence of highly directional interactions. Molecular units of remarkable simplicity self-assemble in solution to give single-molecule thin two-dimensional supramolecular polymers of defined boundaries. This dramatic example spotlights the critical function that topography can have in molecular assembly and paves the path to rationally designed systems of increasing sophistication.

A porphyrin pentamer as a bright emitter for NIR OLEDs.

The luminescence and electroluminescence of an ethyne-linked zinc(ii) porphyrin pentamer have been investigated, by testing blends in two different conjugated polymer matrices, at a range of concentrations. The best results were obtained for blends with the conjugated polymer PIDT-2TPD, at a porphyrin loading of 1 wt%. This host matrix was selected because the excellent overlap between its emission spectrum and the low-energy region of the absorption spectrum of the porphyrin oligomer leads to efficient energy transfer. Thin films of this blend exhibit intense fluorescence in the near-infrared (NIR), with a peak emission wavelength of 886 nm and a photoluminescent quantum yield (PLQY) of 27% in the solid state. Light-emitting diodes (LEDs) fabricated with this blend as the emissive layer achieve average external quantum efficiencies (EQE) of 2.0% with peak emission at 830 nm and a turn-on voltage of 1.6 V. This performance is remarkable for a singlet NIR-emitter; 93% of the photons are emitted in the NIR (λ > 700 nm), indicating that conjugated porphyrin oligomers are promising emitters for non-toxic NIR OLEDs.

Cooperative Weak Dispersive Interactions Actuate Catalysis in a Shape-Selective Abiological Racemase.

A simple abiological host-guest system demonstrates racemase activity with catalytic rate enhancements of 104 without employing traditional functional groups. Cooperative weak interactions enhanced through shape-complementarity between the catalyst active site and the reaction transition state drive this activity, as proposed by Pauling for enzymes. In analogy to the Jencks' concept of catalytic antibodies, it is shown that a hapten resembling the planar transition state of the bowl inversion acts as a potent inhibitor of this catalytic process. In contrast, no substrate/product inhibition is detected, and a relatively weak binding of the substrate is observed (Ka ≈ 102 M-1 at 293 K). This simple box-and-bowl system demonstrates that shape selectivity arising from cooperative dispersive forces suffices for the emergence of a catalytic system with an enzyme-like thermodynamic profile.

Visual Anatomy of an Article - Lessons Learned and Taught in Five Figures.

To grow is to teach. In that spirit this article aims to teach best practice for visualizations and at the same time to highlight some of the harvest we could reap in our lab. Following figures recently published in one of our manuscripts, we demonstrate how creativity in figure making goes hand in hand with storytelling, a deepened understanding of the scientific work and an increase in lateral thinking inside the research avenue. We hope it will help to promote scientific visualizations as a useful, even if sometimes harsh, mirror to give new angles to the laboratory work.

Experimental and Theoretical Evidence for Aromatic Stabilization Energy in Large Macrocycles.

Enhanced thermodynamic stability is a fundamental characteristic of aromatic molecules, yet most previous studies of aromatic stabilization energy (ASE) have been limited to small rings with up to 18 π-electrons. Here we demonstrate that ASE can be detected experimentally in π-conjugated porphyrin nanorings with Hückel circuits of 76-108 π-electrons. This conclusion is supported by analyzing redox potentials to calculate the energy change for isodesmic reactions that convert an aromatic ring to an antiaromatic ring or vice versa. It is also supported by analyzing the energy barriers to conformational equilibria that disrupt aromaticity in the transition state. Both types of experiment indicate that cationic porphyrin nanorings display ASEs of 1-5 kJ mol-1. Density functional theory calculations reproduce the results for both types of experiment and predict ASEs in the range of 1-16 kJ mol-1. The experimental ASEs in porphyrin nanorings are compared with an experimental ASE of [18]annulene of ∼11 kJ mol-1, deduced from analysis of the energy barriers to conformational equilibria in [16], [18], and [20]annulene. Calculated energies of isodesmic reactions give an ASE of ∼37 kJ mol-1 in [18]annulene. This work contributes to a fundamental understanding of aromaticity in large macrocycles.

Bicyclic Phenyl-Ethynyl Architectures: Synthesis of a 1,4-Bis(phenylbuta-1,3-diyn-1-yl) Benzene Banister.

The novel diacetylene bridged terphenylic macrocycle 1 is presented and discussed in the context of rotationally restricted "Geländer" oligomers. The 1,4-bis(phenylbuta-1,3-diyn-1-yl) benzene bridge of diacetylene 1 is significantly longer than its terphenyl backbone, forcing the bridge to bend around the central pylon. The synthesis of molecule 1 is based to a large extent on acetylene scaffolding strategies, profiting from orthogonal alkyne protection groups to close both macrocyclic subunits by oxidative acetylene coupling sequentially. The spatial arrangement and the dynamic enantiomerization process of the bicyclic target structure 1 are analyzed. In-depth NMR investigations not only reveal an unexpected spatial arrangement with both oligomer strands bent alongside the backbone, but also display the limited stability of the model compound in the presence of molecular oxygen.

Allosteric Cooperativity and Template-Directed Synthesis with Stacked Ligands in Porphyrin Nanorings.

The link between allosteric cooperativity and template-directed synthesis has been investigated by studying complexes in which two oligopyridine ligands bind inside a zinc porphyrin nanoring in a stacked arrangement. The binding of a 6-porphyrin nanoring to two tridentate ligands (with s-triazine or benzene cores) occurs with high negative allosteric cooperativity (α ≈ 10-3-10-4). Formation constants for 1:1 and 1:2 complexes were determined by UV-vis-NIR denaturation titration, using pyridine as a competing ligand, and cooperativity factors were confirmed by NMR spectroscopy. The rate constants for formation of the 1:1 and 1:2 complexes are approximately equal, and the negative cooperativity can be attributed to faster dissociation of the 1:2 complex. These tridentate ligands are not effective templates for directing the synthesis of the 6-porphyrin nanoring, in keeping with their negative cooperativity of binding. In contrast, the binding of a 12-porphyrin nanoring to two hexadentate ligands occurs with high positive allosteric cooperativity (α > 40), and the ligand is an effective Vernier template for directing the synthesis of the 12-porphyrin nanoring. This stacked Vernier template approach creates the product in an open circular conformation, which is advantageous for preparing macrocycles that do not easily adopt a figure-of-eight geometry.

Global aromaticity at the nanoscale.

Aromaticity can be defined by the ability of a molecule to sustain a ring current when placed in a magnetic field. Hückel's rule states that molecular rings with [4n + 2] π-electrons are aromatic, with an induced magnetization that opposes the external field inside the ring, whereas those with 4n π-electrons are antiaromatic, with the opposite magnetization. This rule reliably predicts the behaviour of small molecules, typically with fewer than 22 π-electrons (n = 5). It is not clear whether aromaticity has a size limit, or whether Hückel's rule extends to much larger macrocycles. Here, we present evidence for global aromaticity in porphyrin nanorings with circuits of up to 162 π-electrons (n = 40); aromaticity is controlled by changing the constitution, oxidation state and conformation. Whenever a ring current is observed, its direction is correctly predicted by Hückel's rule. The largest ring currents occur when the porphyrin units have fractional oxidation states.

Spin Delocalization in the Radical Cations of Porphyrin Molecular Wires: A New Perspective on EPR Approaches.

The spin delocalization in the radical cations of a series of ethyne-linked oligoporphyrins was investigated using EPR spectroscopy. The room-temperature spectral envelope for these oligomers deviates significantly from the benchmark N-0.5 trend in line width expected for a completely delocalized spin density, in contrast to the butadiyne-linked analogues measured previously. Here, we show, using DFT calculations and complementary low-temperature ENDOR measurements, that this deviation is primarily driven by a more pronounced inequivalence of the 14N spins within individual subunits for the ethyne-linked oligoporphyrins. Once this 14N inequivalence is taken into consideration, the room-temperature and ENDOR spectra for both butadiyne-linked and ethyne-linked oligomers, up to N = 5, can be simulated by similar static delocalization patterns. This work highlights the importance of EPR in exploring such spin delocalization phenomena while also demonstrating that the N-0.5 trend should not be interpreted in isolation but only in combination with careful simulation and theoretical modeling.

Metal Atom Markers for Imaging Epitaxial Molecular Self-Assembly on Graphene by Scanning Transmission Electron Microscopy.

Direct imaging of single molecules has to date been primarily achieved using scanning probe microscopy, with limited success using transmission electron microscopy due to electron beam damage and low contrast from the light elements that make up the majority of molecules. Here, we show single complex molecule interactions can be imaged using annular dark field scanning TEM (ADF-STEM) by inserting heavy metal markers of Pt atoms and detecting their positions. Using the high angle ADF-STEM Z1.7 contrast, combined with graphene as an electron transparent support, we track the 2D monolayer self-assembly of solution-deposited individual linear porphyrin hexamer (Pt-L6) molecules and reveal preferential alignment along the graphene zigzag direction. The epitaxial interactions between graphene and Pt-L6 drive a reduction in the interporphyrin distance to allow perfect commensuration with the graphene. These results demonstrate how single metal atom markers in complex molecules can be used to study large scale packing and chain bending at the single molecule level.

Tuning the Circumference of Six-Porphyrin Nanorings.

Most macrocycles are made from a simple repeat unit, resulting in high symmetry. Breaking this symmetry allows fine-tuning of the circumference, providing better control of the host-guest behavior and electronic structure. Here, we present the template-directed synthesis of two unsymmetrical cyclic porphyrin hexamers with both ethyne (C2) and butadiyne (C4) links, and we compare these nanorings with the symmetrical analogues with six ethyne or six butadiyne links. Inserting two extra carbon atoms into the smaller nanoring causes a spectacular change in binding behavior: the template affinity increases by a factor of 3 × 109, to a value of ca. 1038 M-1, and the mean effective molarity is ca. 830 M. In contrast, removing two carbon atoms from the largest nanoring results in almost no change in its template-affinity. The strain in these nanorings is 90-130 kJ mol-1, as estimated both from DFT calculation of homodesmotic reactions and from comparing template affinities of linear and cyclic oligomers. Breaking the symmetry has little effect on the absorption and fluorescence behavior of the nanorings: the low radiative rates that are characteristic of a circular delocalized S1 excited state are preserved in the low-symmetry macrocycles.

Molecular dynamic staircases: all-carbon axial chiral "Geländer" structures.

Herein, the syntheses of two tightly packed all-carbon "Geländer" molecules with axial chirality are described. Motivated by our previous results, we further reduced the bridge length by excluding the heteroatoms. The absolute configuration was determined by comparison of the measured and calculated circular dichroism (CD) spectra and the thermodynamic stability was determined by dynamic high-performance liquid chromatography (HPLC) and CD analysis. The cyclophanes were fully characterized by CD measurements, X-ray diffraction (XRD) analysis, NMR, UV-Vis and high resolution mass spectrometry (HRMS). Our novel all-carbon macrocycle is the most stable Geländer system reported so far.

Template-Directed Synthesis of a Conjugated Zinc Porphyrin Nanoball.

We report the template-directed synthesis of a π-conjugated 14-porphyrin nanoball. This structure consists of two intersecting nanorings containing six and 10 porphyrin units. Fluorescence upconversion spectroscopy experiments demonstrate that electronic excitation delocalizes over the whole three-dimensional π system in less than 0.3 ps if the nanoball is bound to its templates or over 2 ps if the nanoball is empty.

Single-Acetylene Linked Porphyrin Nanorings.

The synthesis of ethyne-linked porphyrin nanorings has been achieved by template-directed Sonogashira coupling. The cyclic hexamer and octamer are predicted by density functional theory to adopt low symmetry conformations, due to dihedral twists between neighboring porphyrin units, but their symmetries are effectively D6h and D8h, respectively, in solution by 1H NMR. The fluorescence spectra indicate that the singlet excited states of these nanorings are highly delocalized.

Chirality in curved polyaromatic systems.

Carbon allotropes constituted of sp2-hybridised carbon atoms display a variety of properties that arise from their delocalised π-conjugated electronic structure. Apart from carbon's planar allotropic form graphene, bent or curved structures, such as carbon nanotubes or fullerenes, respectively, have been discovered. In this Tutorial Review, we analyse and conceptually categorise chiral synthetic molecular fragments of non-planar sp2-carbon allotropes, including hypothetical forms of carbon that have been proposed to exist as stable entities. Two types of molecular systems composed of equally or differently sized rings are examined: bent with zero Gaussian curvature and curved with positive or negative Gaussian curvature. To affirm that a system is chiral, two conditions must be fulfilled: (1) both reflective symmetry elements, an inversion centre and a mirror plane, must be absent and (2) the system must be stereochemically rigid. It is therefore crucial to not only consider the symmetry of a given system as if it was a rigid object but also its structural dynamics. These principles serve as guidelines for the design of molecular fragments that encode and transcribe chirality into larger systems.