Antiaromatic Dicyclopenta[b,g]/[a,f]naphthalene Isomers Showing an Open-Shell Singlet Ground State with Tunable Diradical Character.

Since the first isolation of 1,3,5,7-tetra-tert-butyl-s-indacene in 1986, core-expanded s- and as-indacenes have attracted intensive interest. However, there is no reported synthesis of such type of molecules due to their high reactivity for over 30 years. Herein, we report the successful synthesis of two relatively stable, core-expanded indacene isomers, dicyclopenta[b,g]-naphthalene (5) and dicyclopenta[a,f]naphthalene (6). X-ray crystallographic analyses reveal that the backbone of 5 adopts a bond-delocalized structure, while that of 6 exhibits a bond-localized character. Variable-temperature 1H NMR/ESR measurements, electronic absorption spectra, and theoretical calculations confirm that both molecules are globally antiaromatic and have an open-shell singlet ground state. However, 6 shows stronger antiaromaticity, a larger diradical character (y0 = 48%), and a smaller singlet-triplet energy gap (ΔES-T = -0.99 kcal mol-1) compared to 5 (y0 = 30%, ΔES-T = -6.88 kcal mol-1), which can be explained by their different quinoidal structures.

Dicyclopenta[4,3,2,1- ghi:4',3',2',1'- pqr]perylene: A Bowl-Shaped Fragment of Fullerene C70 with Global Antiaromaticity.

Solution-phase synthesis of buckybowls remains a big challenge, and there are limited reports on the fragments of C70. Herein, we report a new basic subunit of C70 with C2v symmetry, the dicyclopenta[4,3,2,1- ghi:4',3',2',1'- pqr]perylene (2CP-Per). Its aryl-substituted derivative 2CP-Per-Ar was synthesized and shows a bowl-shaped geometry according to X-ray crystallographic analysis. A fast bowl-to-bowl inversion process was observed above 183 K by variable temperature nuclear magnetic resonance (NMR), with a small inversion energy barrier. 2CP-Per-Ar displays amphoteric redox behavior with a small electrochemical energy gap (1.29 eV). Different from many other aromatic buckybowls, 2CP-Per exhibits global antiaromaticity with a strong paratropic ring current associated with the 16π-electrons rim, as revealed by NMR measurements and theoretic calculations. Its dianion is aromatic, similar to its isoelectronic structure coronene. Its dication is predicted to be aromatic, with a [6]annulene-within-[14]annulene structure.

[6]Cyclo-para-phenylmethine: An Analog of Benzene Showing Global Aromaticity and Open-Shell Diradical Character.

We report a [6]cyclo-para-phenylmethine ([6]CPPM) macrocycle that shows benzene-like electronic properties. Its mesityl derivative, [6]CPPM-Mes, was isolated in crystalline form. X-ray analysis reveals a C2h symmetry, and the bond lengths of the benzenoid/quinoid rings are averaged via resonance. One averaged 1H NMR peak for the protons on the backbone was observed at room temperature, but it was split into one shielded and one deshielded resonance below 198 K, consistent with its globally aromatic character with a dominant 30π conjugation pathway along the periphery. It exhibits open-shell diradical character with a moderate singlet-triplet energy gap (ΔES-T = -6.23 kcal/mol). Its dication is antiaromatic and open-shell, showing a smaller ΔES-T value (-4.18 kcal/mol). Overall, [6]CPPM behaves like an open-shell aromatic "super-benzene".

Long rylene nanoribbons express polyacetylene-like signatures at their edges.

Oligorylenes have been the focus of research during the journey toward intrinsically conducting polyrylene. Recently, the description of diradicaloid and tetraradicaloid properties in long oligorylene molecules has revived the old question about their electronic structures which is of current interest in the context of the properties of graphene nanoribbons. Here we show that the armchair edges of smaller oligorylenes are embedded within aromatic units and they transform into armchair cis-polyacetylenic structures for octarylene and longer. Concomitantly, the short zig-zag edges of oligorylenes stabilize diradicaloid and multiradical states. This electronic transformation is proved experimentally by Raman spectroscopy and supported by theoretical modelling.

Perylene π-Bridges Equally Delocalize Anions and Cations: Proportioned Quinoidal and Aromatic Content.

A complete experimental and theoretical study has been carried out for aromatic and quinoidal perylene-based bridges substituted with bis(diarylamine) and bis(arylimine) groups respectively. The through-bridge inter-redox site electronic couplings (VAB ) have been calculated for their respective mixed-valence radical cation and radical anion species. The unusual similitudes of the resulting VAB values for the given structures reveal the intervention of molecular shapes with balanced semi-quinoidal/semi-aromatic structures in the charge delocalization. An identical molecular object equally responding to the injection of either positive or negative charges is rare in the field of organic π-conjugated molecules. However, once probed herein for perylene-based systems, it can be extrapolated to other π-conjugated bridges. As a result, this work opens the door to the rational design of true ambipolar bulk and molecular conductors.

Superoctazethrene: An Open-Shell Graphene-like Molecule Possessing Large Diradical Character but Still with Reasonable Stability.

Laterally extended zethrenes can be regarded as Z-shaped nanographenes with four zigzag edges, but their synthesis is very challenging. Herein, we report the successful synthesis of by far the largest zethrene molecule, a superoctazethrene (SOZ) derivative SOZ-Cl, in crystalline form. Although the parent SOZ is calculated to have a very large diradical character ( y0 = 81.0%), SOZ-Cl shows reasonable stability ( t1/2 = 64 h under ambient conditions) and can be purified by silica gel column chromatography. It exhibits a small electrochemical energy gap ( Eg = 1.01 eV) and characteristics for open-shell singlet diradicaloids. Compared with a previously reported octazethrene derivative (OZ-TIPS), SOZ-Cl shows much larger diradical character ( y0 = 76.3% vs 43.4%) and smaller singlet-triplet gap (Δ ES-T = -2.30 kcal/mol vs -3.87 kcal/mol). Calculations also demonstrate global aromatic character of SOZ, but the smaller size octazethrene shows local aromaticity.

Stable Nitrogen-Centered Bis(imino)rylene Diradicaloids.

The synthesis of stable open-shell singlet diradicaloids is critical for their practical material application. So far, most reported examples are based on carbon-centered radicals, which are intrinsically reactive, and there are very few examples of stable nitrogen-centered diradicaloids. In this full paper, a series of soluble and stable bis(imino)rylenes up to octarylene were synthesized on the basis of newly developed dibromorylene intermediates. It was found that from hexarylene onward, these quinoidal rylenes showed open-shell singlet ground states and could be thermally populated to paramagnetic triplet aminyl diradicals. They are stable due to efficient spin delocalization onto the rylene backbone as well as kinetic blocking of the aminyl sites by the bulky and electron-deficient 2,4,6-trichlorophenyl groups. They exhibited very different electronic structures, diradical character, excited-state dynamics, one-photon absorption, two-photon absorption, and electrochemical properties from their respective aromatic rylene counterparts. These bis(imino)rylenes represent a rare class of stable, neutral, nitrogen-centered aminyl diradicaloids.

Fluorenyl Based Macrocyclic Polyradicaloids.

Synthesis of stable open-shell polyradicaloids including control of intramolecular spin-spin interactions is a challenging topic in organic chemistry and materials science. Herein, we report the synthesis and physical characterization of two series of fluorenyl based macrocyclic polyradicaloids. In one series (FR-MCn, n = 4-6), the fluorenyl radicals are directly linked at 3,6-positions; whereas in the other series (MC-FnAn, n = 3-5), an additional ethynylene moiety is inserted between the neighboring fluorenyl units. To access stable macrocyclic polyradicaloids, three synthetic methods were developed. All of these stable macrocycles can be purified by normal silica gel column chromatography under ambient conditions. In all cases, moderate polyradical characters were calculated by restricted active space spin-flip method due to the moderate intramolecular antiferromagnetic spin-spin interactions. The excitation energies from the low-spin ground state to the lowest high-spin excited state were evaluated by superconducting quantum interference device measurements. Their physical properties were also compared with the respective linear fluorenyl radical oligomers (FR-n, n = 3-6). It is found that the geometry, i.e., the distortional angle and spacer (w or w/o ethynylene) between the neighboring fluorenyl units, has significant effect on their polyradical character, excitation energy, one-photon absorption, two-photon absorption and electrochemical properties. In addition, the macrocyclic tetramers FR-MC4 and MC-F4A4 showed global antiaromatic character due to cyclic π-conjugation with 36 and 44 π-electrons, respectively.

A Stable N-Annulated Perylene-Bridged Bisphenoxyl Diradicaloid and the Corresponding Boron Trifluoride Complex.

Organic π-extended radicals display unique electronic structures, and could be used as promising functional materials. However, design and synthesis of stable radicals are challenging for chemists due to their high reactivity. In this work, we synthesized a stable N-annulated perylene-bridged bisphenoxyl diradicaloid, and its complex with Lewis acid boron trifluoride. Their ground-state geometric and electronic structures were systematically studied by various experimental methods, including X-ray crystallographic analysis, variable-temperature NMR spectroscopy, electron-spin resonance spectroscopy (ESR), and superconducting quantum interference device (SQUID) measurements, supported by density functional theory. Both were observed as open-shell singlet diradicaloids in the ground state. The bisphenoxyl diradicaloid demonstrated string features of strong near-infrared (NIR) absorption, closely packed π-dimer structure in crystals, amphoteric redox behavior with a small HOMO-LUMO energy band gap, and a rather small singlet-triplet gap, whereas the complex showed very different photophysical, electrochemical, and magnetic properties. Our studies provide an efficient method of making stable diradicaloids by Lewis acid/base complexation.

Ambient Stable Radical Cations, Diradicaloid π-Dimeric Dications, Closed-Shell Dications, and Diradical Dications of Methylthio-Capped Rylenes.

Radical cations and dications of π-conjugated systems play vital roles in organic electronic devices, organic conductors, and conducting polymers. Their structures, charge and spin distribution, and mechanism of charge transport are of great interest. In this article, radical cations and dications of a series of newly synthesized methylthio-capped rylenes were synthesized and isolated. Their ground-state structures, physical properties, and solid-state packing were systematically investigated by various experimental methods, such as X-ray crystallographic analysis, UV/Vis/NIR absorption spectroscopy, (spectro-)electrochemistry, nuclear magnetic resonance spectroscopy, electron spin resonance spectroscopy, superconducting quantum interference device, and Raman spectroscopy, assisted by DFT calculations. It was found that all the charged species show an exceptional stability under ambient air and light conditions due to the efficient spin and charge delocalization over the whole rylene backbone. The dication of hexarylene turned out to have an unusual open-shell singlet rather than closed-shell ground state, thus it can be described as a diradical dication. Dimerization was observed for the radical cations and even the dications in crystals due to the strong intermolecular antiferromagnetic spin-spin interaction and π-π interaction, which result in unique magnetic properties. Such intermolecular association was also observed in solution.

Conformationally Flexible Bis(9-fluorenylidene)porphyrin Diradicaloids.

A stable 5,10-bis(9-fluorenylidene)porphyrin (Por-Fl) diradicaloid was synthesized. It shows a quinoidal, saddle-shaped geometry in the single crystal but can be thermally populated to a triplet diradical both in solution and in the solid state. Coordination with the Ni2+ ion (Por-Fl-Ni) does not significantly change the contorted conformation but reduces the singlet-triplet gap. Heat-induced geometric change can explain the observed paramagnetic properties as well as unusual hysteresis in SQUID measurements. On the other hand, protonation (Por-Fl-2H+ ) dramatically changes the conformation while maintains the closed-shell electronic structure. Our studies demonstrate how heat, coordination, and protonation affect the geometry, diradical character, and physical properties of conformationally flexible open-shell singlet diradicaloids.

Toward Stable Superbenzoquinone Diradicaloids.

Superbenzoquinone (SBQ) is a quinone derived from a classic polycyclic aromatic hydrocarbon (PAH), hexa-peri-hexabenzocoronene (so-called "superbenzene"), and is a challenging synthetic target. Herein we report the successful synthesis and characterization of its derivatives. We reveal that the high reactivity of SBQ is due to its intrinsic open-shell diradical character. Thus, two kinetically blocked SBQs, SBQ-Me and SBQ-Ph, were prepared by different synthetic strategies. 4-tert-Butylphenyl-substituted SBQ-Ph demonstrated good stability and could be isolated in crystalline form. Both compounds have an open-shell singlet ground state and show thermally populated paramagnetic activity. Our studies provide effective strategies toward stable quinone-based diradicaloids.

Higher Order π-Conjugated Polycyclic Hydrocarbons with Open-Shell Singlet Ground State: Nonazethrene versus Nonacene.

Higher order acenes (i.e., acenes longer than pentacene) and extended zethrenes (i.e., zethrenes longer than zethrene) are theoretically predicted to have an open-shell singlet ground state, and the radical character is supposed to increase with extension of molecular size. The increasing radical character makes the synthesis of long zethrenes and acenes very challenging, and so far, the longest reported zethrene and acene derivatives are octazethrene and nonacene, respectively. In addition, there is a lack of fundamental understanding of the differences between these two closely related open-shell singlet systems. In this work, we report the first synthesis of a challenging nonazethrene derivative, HR-NZ, and its full structural and physical characterizations including variable temperature NMR, ESR, SQUID, UV-vis-NIR absorption and electrochemical measurements. Compound HR-NZ has an open-shell singlet ground state with a moderate diradical character (y0 = 0.48 based on UCAM-B3LYP calculation) and a small singlet-triplet gap (ΔES-T = -5.2 kcal/mol based on SQUID data), thus showing magnetic activity at room temperature. It also shows amphoteric redox behavior, with a small electrochemical energy gap (1.33 eV). Its electronic structure and physical properties are compared with those of Anthony's nonacene derivative JA-NA and other zethrene derivatives. A more general comparison between higher order acenes and extended zethrenes was also conducted on the basis of ab initio electronic structure calculations, and it was found that zethrenes and acenes have very different spatial localization of the unpaired electrons. As a result, a faster decrease of singlet-triplet energy gap and a faster increase of radical character with increase of the number of benzenoid rings were observed in zethrene series. Our studies reveal that spatial localization of the frontier molecular orbitals play a very important role on the nature of radical character as well as the excitation energy.

Super-heptazethrene.

The challenging synthesis of a laterally extended heptazethrene molecule, the super-heptazethrene derivative SHZ-CF3, is reported. This molecule was prepared using a strategy involving a multiple selective intramolecular Friedel-Crafts alkylation followed by oxidative dehydrogenation. Compound SHZ-CF3 exhibits an open-shell singlet diradical ground state with a much larger diradical character compared with the heptazethrene derivatives. An intermediate dibenzo-terrylene SHZ-2H was also obtained during the synthesis. This study provides a new synthetic method to access large-size quinoidal polycyclic hydrocarbons with unique physical properties.

N-annulated perylene-substituted and fused porphyrin dimers with intense near-infrared one-photon and two-photon absorption.

Fusion of two N-annulated perylene (NP) units with a fused porphyrin dimer along the S0-S1 electronic transition moment axis has resulted in new near-infrared (NIR) dyes 1 a/1 b with very intense absorption (ε>1.3×10(5) M(-1) cm(-1)) beyond 1250 nm. Both compounds displayed moderate NIR fluorescence with fluorescence quantum yields of 4.4×10(-6) and 6.0×10(-6) for 1 a and 1 b, respectively. The NP-substituted porphyrin dimers 2 a/2 b have also been obtained by controlled oxidative coupling and cyclodehydrogenation, and they showed superimposed absorptions of the fused porphyrin dimer and the NP chromophore. The excited-state dynamics of all of these compounds have been studied by femtosecond transient absorption measurements, which revealed porphyrin dimer-like behaviour. These new chromophores also exhibited good nonlinear optical susceptibility with large two-photon absorption cross-sections in the NIR region due to extended π-conjugation. Time-dependent density functional theory calculations have been performed to aid our understanding of their electronic structures and absorption spectra.

N-annulated perylene as an efficient electron donor for porphyrin-based dyes: enhanced light-harvesting ability and high-efficiency Co(II/III)-based dye-sensitized solar cells.

Porphyrin-based dyes recently have become good candidates for dye-sensitized solar cells (DSCs). However, the bottleneck is how to further improve their light-harvesting ability. In this work, N-annulated perylene (NP) was used to functionalize the Zn-porphyrin, and four "push-pull"-type NP-substituted and fused porphyrin dyes with intense absorption in the visible and even in the near-infrared (NIR) region were synthesized. Co(II/III)-based DSC device characterizations revealed that dyes WW-5 and WW-6, in which an ethynylene spacer is incorporated between the NP and porphyrin core, showed pantochromatic photon-to-current conversion efficiency action spectra in the visible and NIR region, with a further red-shift of about 90 and 60 nm, respectively, compared to the benchmark molecule YD2-o-C8. As a result, the short-circuit current density was largely increased, and the devices displayed power conversion efficiencies as high as 10.3% and 10.5%, respectively, which is comparable to that of the YD2-o-C8 cell (η = 10.5%) under the same conditions. On the other hand, the dye WW-3 in which the NP unit is directly attached to the porphyrin core showed a moderate power conversion efficiency (η = 5.6%) due to the inefficient π-conjugation, and the NP-fused dye WW-4 exhibited even poorer performance due to its low-lying LUMO energy level and nondisjointed HOMO/LUMO profile. Our detailed physical measurements (optical and electrochemical), density functional theory calculations, and photovoltaic characterizations disclosed that the energy level alignment, the molecular orbital profile, and dye aggregation all played very important roles on the interface electron transfer and charge recombination kinetics.

para-Quinodimethane-bridged perylene dimers and pericondensed quaterrylenes: the effect of the fusion mode on the ground states and physical properties.

Polycyclic hydrocarbon compounds with a singlet biradical ground state show unique physical properties and promising material applications; therefore, it is important to understand the fundamental structure/biradical character/physical properties relationships. In this study, para-quinodimethane (p-QDM)-bridged quinoidal perylene dimers 4 and 5 with different fusion modes and their corresponding aromatic counterparts, the pericondensed quaterrylenes 6 and 7, were synthesized. Their ground-state electronic structures and physical properties were studied by using various experiments assisted with DFT calculations. The proaromatic p-QDM-bridged perylene monoimide dimer 4 has a singlet biradical ground state with a small singlet/triplet energy gap (-2.97 kcal mol(-1)), whereas the antiaromatic s-indacene-bridged N-annulated perylene dimer 5 exists as a closed-shell quinoid with an obvious intramolecular charge-transfer character. Both of these dimers showed shorter singlet excited-state lifetimes, larger two-photon-absorption cross sections, and smaller energy gaps than the corresponding aromatic quaterrylene derivatives 6 and 7, respectively. Our studies revealed how the fusion mode and aromaticity affect the ground state and, consequently, the photophysical properties and electronic properties of a series of extended polycyclic hydrocarbon compounds.

Pushing extended p-quinodimethanes to the limit: stable tetracyano-oligo(N-annulated perylene)quinodimethanes with tunable ground states.

p-Quinodimethane (p-QDM) is a fundamental building block for the design of π-conjugated systems with low band gap and open-shell biradical character. However, synthesis of extended p-QDMs has usually suffered from their intrinsic high reactivity and poor solubility. In this work, benzannulation together with terminal cyano-substitution was demonstrated to be an efficient approach for the synthesis of a series of soluble and stable tetracyano-oligo(N-annulated perylene)quinodimethanes nPer-CN (n = 1-6), with the longest molecule having 12 para-linked benzenoid rings! The geometry and electronic structures of these oligomers were investigated by steady-state and transient absorption spectroscopy, nuclear magnetic resonance, electron spin resonance, superconducting quantum interference device, and FT Raman spectroscopy assisted by density functional theory calculations. They showed tunable ground states, varying from a closed-shell quinoidal structure for monomer, to a singlet biradical for dimer, trimer, and tetramer, and to a triplet biradical for pentamer and hexamer. Large two-photon absorption cross-section values were observed in the near-infrared range, which also exhibited a clear chain-length dependence.

A p-quinodimethane-bridged porphyrin dimer.

A p-quinodimethane (p-QDM)-bridged porphyrin dimer 1 has been prepared for the first time. An unexpected Michael addition reaction took place when we attempted to synthesize compound 1 by reaction of the cross-conjugated keto-linked porphyrin dimers 8a and 8b with alkynyl/aryl Grignard reagents. Alternatively, compound 1 could be successfully prepared by intramolecular Friedel-Crafts alkylation of the diol-linked porphyrin dimer 14 with concomitant oxidation in air. Compound 1 shows intense one-photon absorption (OPA, λ(max)=955 nm, ε=45400 M(-1) cm(-1)) and a large two-photon absorption (TPA) cross-section (σ((2))(max)=2080 GM at 1800 nm) in the near-infrared (NIR) region due to its extended π-conjugation and quinoidal character. It also exhibits a short singlet excited-state lifetime of 25 ps. The cyclic voltammogram of 1 displays multiple redox waves with a small electrochemical energy gap of 0.86 eV. The ground-state geometry, electronic structure, and optical properties of 1 have been further studied by density functional theory (DFT) calculations and compared with those of the keto-linked dimer 8b. This research has revealed that incorporation of a p-QDM unit into the porphyrin framework had a significant impact on its optical and electronic properties, leading to a novel NIR OPA and TPA chromophore.

Stable tetrabenzo-Chichibabin's hydrocarbons: tunable ground state and unusual transition between their closed-shell and open-shell resonance forms.

Stable open-shell polycyclic aromatic hydrocarbons (PAHs) are of fundamental interest due to their unique electronic, optical, and magnetic properties and promising applications in materials sciences. Chichibabin's hydrocarbon as a classical open-shell PAH has been investigated for a long time. However, most of the studies are complicated by their inherent high reactivity. In this work, two new stable benzannulated Chichibabin's hydrocarbons 1-CS and 2-OS were prepared, and their electronic structure and geometry in the ground state were studied by various experiments (steady-state and transient absorption spectra, NMR, electron spin resonance (ESR), superconducting quantum interference device (SQUID), FT Raman, X-ray crystallographic etc.) and density function theory (DFT) calculations. 1-CS and 2-OS exhibited tunable ground states, with a closed-shell quinoidal structure for 1-CS and an open-shell biradical form for 2-OS. Their corresponding excited-state forms 1-OS and 2-CS were also chemically approached and showed different decay processes. The biradical 1-OS displayed an unusually slow decay to the ground state (1-CS) due to a large energy barrier (95 ± 2.5 kJ/mol) arising from severe steric hindrance during the transition from an orthogonal biradical form to a butterfly-like quinoidal form. The quick transition from the quinoidal 2-CS (excited state) to the orthogonal biradicaloid 2-OS (ground state) happened during the attempted synthesis of 2-CS. Compounds 1-CS and 2-OS can be oxidized into stable dications by FeCl(3) and/or concentrated H(2)SO(4). The open-shell 2-OS also exhibited a large two-photon absorption (TPA) cross section (760 GM at 1200 nm).