Conformational, Structural, and Chiroptical Properties of an Overcrowded Triply Fused Carbo[7]helicene.

Recently, the synthesis of the racemate of an overcrowded triply fused carbo[7]helicene of formula C66H36 with three carbo[7]helicenes fused within a central six-membered ring was described. This molecule was found to embed an extremely contorted central six-membered ring and two negative curvatures. We report herein the resolution of the corresponding enantiomers and their conformational, structural, photophysical, and chiroptical properties. The racemization of the triply fused carbo[7]helicene was determined to proceed at a rate of krac = 8.06 × 10-4 s-1 at 175 °C in ortho-dichlorobenzene, corresponding to a barrier to enantiomerization ΔGenant‡ = 140.4 kJ·mol-1, a value significantly lower than for pristine carbo[7]helicene. Interestingly, the crystalline structures of the racemic and enantiopure materials show some differences regarding the molecular geometry, with an increased negative curvature in the latter cases. This unusual curved delocalized π-conjugated system afforded notably green fluorescence at room temperature and far-red phosphorescence at low temperature. Finally, electronic circular dichroism and circularly polarized luminescence responses of the enantiopure compounds have been measured and showed very close absorption and emission dissymmetry factors, gabs and glum, respectively, of ca. 2.6 × 10-3, indicating a similar chiral rigid geometry for both ground and excited states.

Modulation of Chiroptical and Photophysical Properties in Helicenic Rhenium(I) Systems: The Use of an N-(Aza[6]helicenyl)-NHC Ligand.

The photophysical and chiroptical properties of a novel, chiral helicene-NHC-Re(I) complex bearing an N-(aza[6]helicenyl)-benzimidazolylidene ligand are described, showing its ability to emit yellow circularly polarized luminescence. A comparative analysis of this new system with other helicene-Re(I) complexes reported to date illustrates the impact of structural modifications on the emissive and absorptive properties.

Recent advances in room temperature phosphorescence of chiral organic materials.

Room temperature phosphorescence (RTP) in purely organic materials is an uncommon phenomenon of emission, which can be characterized by a long persistent luminescence after removal of the excitation source. In the recent years, RTP organic materials have received a considerable attention due to their high application potential in various advancing technologies, ranging from optoelectronic to biomedical applications. In parallel, many progresses have been achieved on the rationalization of this process and led to the emergence of innovative strategies aiming to achieve highest performances both in terms of phosphorescence efficiency and lifetime. While the topic is still on an ascendant development, the generation of circularly polarized phosphorescent (CPP) emission from purely organic molecules is by far much less explored and remains an impressive challenge. Still, the perspective of CPP materials appears as an interesting opportunity to answer several comprehensives issues existing in the field. In this article, we define, in a straightforward way, basic principles and key notions for the generation of RTP and CP luminescence (CPL) guiding the design toward CPP materials. After this brief insight, recent advances in the field of chiral organic RTP materials are discussed with an emphasis on their CP-RTP properties. Based on this development, the conclusion drawn allows establishing the next challenges and future opportunities standing in the field.

Circularly Polarized Luminescence from Cyclic (Alkyl)(Amino) Carbene Derived Propellers.

Organic circularly polarized luminescence (CPL)-active molecular emitters featuring dynamic propeller-like luminophores were prepared in one step from cyclic(alkyl)(amino) carbenes (CAACs). These molecules exhibit through-space arene-arene π-delocalization and rapid intramolecular inter-system crossing (ISC) in line with their helical character.

Carbazole Isomerism in Helical Radical Cations: Spin Delocalization and SOMO-HOMO Level Inversion in the Diradical State.

We report a new molecular design to afford persistent chiral organic open-shell systems with configurational stability and an inversion in energy of the singly occupied molecular orbital (SOMO) and the highest doubly occupied molecular orbital (HOMO) for both mono- and diradical states. The unpaired electron delocalization within the designed extended helical π-conjugated systems is a crucial factor to reach chemical stabilities, which is not obtained using the classical steric protection approach. The unique features of the obtained helical monoradicals allow an exploration of the chiral intramolecular electron transfer (IET) process in solvents of different polarity by means of optical and chiroptical spectroscopies, resulting in an unprecedented electronic circular dichroism (ECD) sign inversion for the radical transitions. We also characterized the corresponding helical diradicals, which show near-infrared electronic circular dichroism at wavelengths up to 1100 nm and an antiferromagnetic coupling between the spins, with an estimated singlet-triplet gap (ΔEST) of about -1.2 kcal mol-1. The study also revealed an intriguing double SOMO-HOMO inversion (SHI) electronic configuration for these diradicals, providing new insight regarding the peculiar energetic ordering of radical orbitals and the impact on the corresponding (chiral) optoelectronic properties.

Planar Chiral Analogues of PRODAN Based on a [2.2]Paracyclophane Scaffold: Synthesis and Photophysical Studies.

We describe the synthesis and photophysical characterization of differently substituted planar chiral analogues of PRODAN based on a [2.2]paracyclophane scaffold. This experimental and theoretical study highlights that the (chir)optical properties of the new "phane" compounds, which incorporate an electron-withdrawing propionyl moiety and an electron-donating dimethylamino group at their para or pseudo-para positions, strongly depend on their substitution patterns. In particular, for this series of molecules, a more pronounced solvatochromism and clear chiroptical behaviors are observed when the two substituents are placed on the two rings of the pCp core in a non-"co-planar" arrangement (pseudo-para derivative). This observation may help design new pCp-based luminophores with finely tuned photophysical properties.

Simultaneous Detection of Circularly Polarized Luminescence and Raman Optical Activity in an Organic Molecular Lemniscate.

Circularly polarized luminescence (CPL) and Raman optical activity (ROA) were observed in a single spectroscopic experiment for a purely organic molecule, an event that had so far been limited to lanthanide-based complexes. The present observation was achieved for [16]cycloparaphenylene lemniscate, a double macrocycle constrained by a rigid 9,9'-bicarbazole subunit, which introduces a chirality source and allows the molecule to be resolved into two configurationally stable enantiomers. Distortion of oligophenylene loops in this lemniscular structure produces a large magnetic transition dipole moment while maintaining the π-conjugation-induced enhancement of the Raman signal, causing the appearance of the CPL/ROA couple. A two-photon mechanism is proposed to explain the population of the lowest-energy excited electronic state prior to the simultaneous emission-scattering event.

Luminescent Chiral Exciplexes with Sky-Blue and Green Circularly Polarized-Thermally Activated Delayed Fluorescence.

Luminescent exciplexes based on a chiral electron donor and achiral acceptors are reported as a new approach to design circularly polarized (CP) and thermally activated delayed fluorescence (TADF) emitters. This strategy results in rather high CP luminescence (CPL) values with glum up to 7×10-3 , one order of magnitude higher in comparison to the CPL signal recorded for the chiral donor alone (glum ∼7×10-4 ). This increase occurs concomitantly with a CPL sign inversion, as a result of the strong charge-transfer emission character, as experimentally and theoretically rationalized by using a covalent chiral donor-acceptor model. Interestingly, blue, green-yellow and red chiral luminescent exciplexes can be obtained by modifying with the electron accepting character of the achiral unit while keeping the same chiral donor unit. These results bring new (inter)molecular guidelines to obtain simply and efficiently multi-color CP-TADF emitters.

Rhodium-Catalyzed Enantioselective Synthesis of Highly Fluorescent and CPL-Active Dispiroindeno[2,1-c]fluorenes.

The enantioselective synthesis of chiral [7]-helical dispirodihydro[2,1-c]indenofluorenes (DSF-IFs) was achieved for the first time in good yields with high er values (er up to 99 : 1). The crucial step of the whole reaction sequence was the enantioselective intramolecular [2+2+2] cycloaddition of tethered triynediols to indenofluorenediols, which was catalyzed by a Rh/SEGPHOS® complex. Further transformations led to the corresponding DSF-IFs. The prepared helically chiral DSF-IFs combine circularly polarized luminescence (CPL) activity (glum =∼10-3 ) with exceptionally high fluorescence quantum yields (up to Φlum =0.97).

Enantioenriched Helicenes and Helicenoids Containing Main-Group Elements (B, Si, N, P).

In this review, we discuss the rich chemistry of helicenes and helicenoids containing main-group elements. Enantioenriched helicenic derivatives containing main-group elements B, Si, N, and P, either incorporated within the helical backbone or grafted to it, will be thoroughly presented. We will describe their synthesis, resolution, and asymmetric synthesis, their structural features, electronic and chiroptical properties, and emission, together with other photochemical properties and applications.

Axially and Helically Chiral Cationic Radical Bicarbazoles: SOMO-HOMO Level Inversion and Chirality Impact on the Stability of Mono- and Diradical Cations.

We report persistent chiral organic mono- and diradical cations based on bicarbazole molecular design with an unprecedented stability dependence on the type of chirality, namely, axial versus helical. An unusual chemical stability was observed for sterically unprotected axial bicarbazole radical in comparison with monocarbazole and helical bicarbazole ones. Such results were experimentally and theoretically investigated, revealing an inversion in energy of the singly occupied molecular orbital (SOMO) and the highest (doubly) occupied molecular orbital (HOMO) in both axial and helical bicarbazole monoradicals along with a subtle difference of electronic coupling between the two carbazole units, which is modulated by their relative dihedral angle and related to the type of chirality. Such findings allowed us to explore in depth the SOMO-HOMO inversion (SHI) in chiral radical molecular systems and provide new insights regarding its impact on the stability of organic radicals. Finally, these specific electronic properties allowed us to prepare a persistent, intrinsically chiral, diradical which notably displayed near-infrared electronic circular dichroism responses up to 1100 nm and almost degenerate singlet-triplet ground states with weak antiferromagnetic interactions evaluated by magnetometry experiments.

Maximizing Chiral Perturbation on Thermally Activated Delayed Fluorescence Emitters and Elaboration of the First Top-Emission Circularly Polarized OLED.

Molecular designs merging circularly polarized luminescence (CPL) and thermally activated delayed fluorescence (CP-TADF) using the concept of chiral perturbation appeared recently as a cornerstone for the development of efficient CP-organic light emitting diodes (CP-OLED). Such devices could strongly increase the energy efficiency and performances of conventional OLED displays, in which 50% of the emitted light is often lost due to the use of antiglare filters. In this context, herein, ten couples of enantiomers derived from novel chiral emitter designs are reported, exhibiting CPL, TADF, and aggregation induced enhancement emission properties (AIEE). Representing the first structure properties relationship investigation for CP-TADF materials, this thorough experimental and theoretical work highlights crucial findings on the key structural and electronic parameters (isomerism, nature of the carbazole substituents) governing the synergy between CPL and TADF properties. To conclude this study, the first top emission CP-OLED is elaborated as a new approach of generating CP light in comparison with classical bottom-emission CP-OLED architecture. Indeed, the top-emission configuration represents the only relevant device architecture for future microdisplay applications. Thereby, in addition to offer molecular guidelines to combine efficiently TADF and CPL properties, this study opens new avenues toward practical applications for CP-OLEDs.

Long-Lived Circularly Polarized Phosphorescence in Helicene-NHC Rhenium(I) Complexes: The Influence of Helicene, Halogen, and Stereochemistry on Emission Properties.

The first enantiopure chiral-at-rhenium complexes of the form fac-ReX(CO)3 (:C^N) have been prepared, where :C^N is a helicene-N-heterocyclic carbene (NHC) ligand and X=Cl or I. These have complexes show strong changes in the emission characteristics, notably strongly enhanced phosphorescence lifetimes (reaching 0.7 ms) and increased circularly polarized emission (CPL) activity, as compared to their parent chiral models lacking the helicene unit. The halogen along with its position within the dissymmetric stereochemical environment strongly affect the photophysics of the complexes, particularly the phosphorescence quantum yield and lifetime. These results give fresh insight into fine tuning of photophysical and chiroptical properties of Re-NHC systems.

Bipyrrole boomerangs via Pd-mediated tandem cyclization-oxygenation. Controlling reaction selectivity and electronic properties.

Boomerang-shaped bipyrroles containing donor-acceptor units were obtained through a tandem palladium-mediated reaction consisting of a cyclization step, involving double C-H bond activation, and a double α-oxygenation. The latter reaction can be partly suppressed for the least reactive systems, providing access to α-unsubstituted boomerangs for the first time. These "α-free" systems are highly efficient fluorophores, with emission quantum yields exceeding 80% in toluene. Preliminary measurements show that helicene-like boomerangs may be usable as circularly polarized luminescent materials.

Lemniscular [16]Cycloparaphenylene: A Radially Conjugated Figure-Eight Aromatic Molecule.

A cycloparaphenylene-based molecular lemniscate (CPPL) was obtained in a short synthesis involving masked p-phenylene equivalents. The strained figure-eight geometry of CPPL is sustained by the incorporated 9,9'-bicarbazole subunit, which also acts as a stereogenic element. The shape of the distorted [16]cycloparaphenylene nanohoop embedded in CPPL is accurately approximated with a Booth lemniscate. The structure of CPPL, investigated using NMR and Raman spectroscopic methods, revealed strain-dependent features, consistent with the variable curvature of the ring. The electronic and optical properties of CPPL combine features more characteristic of smaller cycloparaphenylenes, such as a reduced optical bandgap and red-shifted fluorescence. CPPL was resolved into enantiomers, which are configurationally stable and provide strong chiroptical responses, including circularly polarized luminescence.

3D Coumarin Systems Based on [2.2]Paracyclophane: Synthesis, Spectroscopic Characterization, and Chiroptical Properties.

In this article, we report the preparation of a series of [2.2]paracyclophane-fused coumarin systems through a simple and general procedure involving a transition-metal-catalyzed cyclization of aryl alkynoates as the key step. We also highlight the influence of the [2.2]paracyclophane (pCp) motif and its "phane" interactions on the spectroscopic properties of the newly synthesized fluorophores, which emit in the blue-green region of the visible spectrum (λem up to 560 nm) and show extremely large Stokes shifts (up to 230 nm). Finally, we demonstrate that our straightforward approach can easily be used to access optically active planar chiral 3D coumarins. Compared to previously described fluorescent paracyclophanes and other organic dyes, our compact heteroaromatic derivatives show promising chiroptical properties, both in term of circular dichroism ( gabs ∼ 8 × 10 -3) and circularly polarized luminescence ( glum ∼ 5 × 10 -3), thus demonstrating a practical application of our synthetic method.

Bis-4-aza[6]helicene: A Bis-helicenic 2,2'-Bipyridine with Chemically Triggered Chiroptical Switching Activity.

A novel enantiopure bis-helicenic 2,2'-bipyridine system was prepared using a Negishi coupling. Thanks to the bipyridine unit, the coordination with ZnII and protonation processes were studied, revealing efficient tuning of photophysical (UV/visible and emission) and chiroptical properties (electronic circular dichroism and circularly polarized emission) of the system. The coordination/decoordination and protonation/deprotonation processes appeared reversible, thus constituting novel chiroptical switches.

Tetrathiafulvalene-Based Helicene Ligand in the Design of a Dysprosium Field-Induced Single-Molecule Magnet.

The design of a coordination complex that involves a ligand combining both a tetrathiafulvalene core and a helicene fragment was achieved thanks to the reaction between the new 2-{1-[2-methyl[6]helicene]-4,5-[4,5-bis(propylthio)tetrathiafulvalenyl]-1 H-benzimidazol-2-yl}pyridine ligand (L) and the Dy(hfac)3·2H2O metalloprecursor. Magnetic investigations showed field-induced single-molecule-magnet (SMM) behavior under an applied magnetic field of 1000 Oe for [Dy(hfac)3(L)]·0.5CH2Cl2, while experimentally oriented single-crystal magnetic measurements allowed for determination of the magnetic anisotropy orientation. The magnetic behavior was rationalized through ab initio CASSCF/SI-SO calculations. This redox-active chiral-field-induced SMM paves the way for the design of switchable-multiproperty SMMs.

Synthesis and chiroptical properties of organometallic complexes of helicenic N-heterocyclic carbenes.

Novel [4, 6]helicenes (4a,b) bearing a fused imidazolium unit have been prepared from [4, 6]helicene-2,3-di-n-propyl-amines 3a,b. The in situ formation of N-heterocyclic carbene (NHC) derivatives followed by their complexation to iridium(I) or rhodium(I) gave access to complexes 1a, 1'a, and 1b, containing mono-coordinated helicene-NHC, chloro and COD (COD = 1,5-cyclooctadiene) ligands. Ir and Rh complexes 1a and 1'a were characterized by X-ray crystallography. HPLC and NMR analyses showed that Ir(I) complex 1b existed as a mixture of two diastereomeric complexes corresponding to enantiomeric pairs M-(-)/P-(+)-1b1 and M-(-)/P-(+)-1b2 which differ by the position of COD through space. The chiroptical properties (electronic circular dichroism and optical rotation) of the four stereoisomers were measured. These complexes were also tested as catalysts in a transfer hydrogenation reaction.

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.