Controlling Regioselectivity in Palladium-Catalyzed C-H Activation/Aryl-Aryl Coupling of 4-Phenylamino[2.2]paracyclophane.

Selective activation/functionalization of C-H bonds has emerged as an atom- and step-economical process at the forefront of modern synthetic chemistry. This work reports palladium-catalyzed exclusively para-selective C-H activation/aryl-aryl bond formation with a preference over N-arylation under the Buchwald-Hartwig amination reaction of 4-phenylamino[2.2]paracyclophane. This innovative synthetic strategy allows a facile preparation of [2.2]paracyclophane derivatives featuring disparate para-substitutions at C-4 and C-7 positions in a highly selective manner, gives access to a series of potential candidates for [2.2]paracyclophane-derived new planar chiral ligands. The unprecedented behavior in reactivity and preferential selectivity of C-C coupling over C-N bond formation via C-H activation is unique to the [2.2]paracyclophane scaffold compared to the non-cyclophane analogue under the same reaction conditions. Selective C-H activation/aryl-aryl bond formation and sequential C-N coupling product formation is evidenced unambiguously by X-ray crystallography.

Regioselective Functionalization of [2.2]Paracyclophanes: Recent Synthetic Progress and Perspectives.

[2.2]Paracyclophane (PCP) is a prevalent scaffold that is widely utilized in asymmetric synthesis, π-stacked polymers, energy materials, and functional parylene coatings that finds broad applications in bio- and materials science. In the last few years, [2.2]paracyclophane chemistry has progressed tremendously, enabling the fine-tuning of its structural and functional properties. This Minireview highlights the most important recent synthetic developments in the selective functionalization of PCP that govern distinct features of planar chirality as well as chiroptical and optoelectronic properties. Special focus is given to the function-inspired design of [2.2]paracyclophane-based π-stacked conjugated materials by transition-metal-catalyzed cross-coupling reactions. Current synthetic challenges, limitations, as well as future research directions and new avenues for advancing cyclophane chemistry are also summarized.

Planar chiral [2.2]paracyclophanes: from synthetic curiosity to applications in asymmetric synthesis and materials.

Planar chiral [2.2]paracyclophane-based ligands and employment of such enantiopure representative ligands to facilitate selective transformation of prochiral or racemic substances into enantiopure products are rarely explored compared to the complex chiral scaffolds such as ferrocenes. This tutorial discusses recent findings and inspiring progress in design, synthetic tunability and applications of planar chiral [2.2]paracyclophane systems as a practical class of catalysts for asymmetric synthesis. Here, we summarize a series of planar chiral [2.2]paracyclophanes that are becoming an important new tool-box in asymmetric synthesis, employed in a variety of synthetic venues such as new chiral ligands and catalysts for stereo-controlled and enantioselective addition of alkyl, alkenyl, alkynyl and aryl zinc reagents to aliphatic and aromatic aldehydes, ketones, imines and many more. Besides, planar chiral [2.2]paracyclophanes are useful synthons, from a material perspective, can be incorporated into conjugated polymeric systems for chiroptical and optoelectronic properties, find broad applications in bio- and materials science, for instance, gold-based cytostatics, surface-mounted chiral MOF thin films for selective adsorption or in functionalized parylene polymer coatings, to name a few. This is an up-to-date tutorial review, written exclusively on planar chiral [2.2]paracyclophane chemistry, covering key aspects of synthesis, structures, properties, applications and future directions of chiral polymeric assemblies and novel biomaterials built with [2.2]paracyclophanes.

Propellanes-From a Chemical Curiosity to "Explosive" Materials and Natural Products.

Propellanes are a unique class of compounds currently consisting of well over 10 000 representatives, all featuring two more or less inverted tetrahedral carbon atoms that are common to three bridging rings. The central single bond between the two bridgeheads is significantly weakened in the smaller entities, which leads to unusual reactivities of these structurally interesting propeller-like molecules. This Review highlights the synthesis of such propellanes and their occurrence in material sciences, natural products, and medicinal chemistry. The conversion of [1.1.1]propellane into bridgehead derivatives of bicyclo[1.1.1]pentane, including oligomers and polymers with bicyclo[1.1.1]penta-1,3-diyl repeat units, is also featured. A selection of natural products with larger propellane subunits are discussed in detail. Heteropropellanes and inorganic propellanes are also addressed. The historical background is touched in brief to show the pioneering work of David Ginsburg, Günther Snatzke, Kenneth B. Wiberg, Günter Szeimies, and others.

Efficient deep-blue luminescence based on dual-channel intra/intermolecular exciplexes.

Highly efficient and stable blue organic light-emitting diodes (OLEDs) cannot be easily obtained simultaneously. In particular, the efficiency roll-off as a reference index to evaluate the lifetime of deep-blue OLED at high luminescence is still severe. A novel molecule (CzSiTrz) connected with carbazole and triazine fragments by a nonconjugated silicon atom is designed. An intramolecular charge transfer emission and intermolecular exciplex luminescence in the aggregated state are obtained, resulting in a dual-channel intra/intermolecular exciplex (DCIE) emission with fast and efficient reverse intersystem crossing (RISC). Deep-blue OLED with Commission Internationale de l'Eclairage (CIE) coordinates of (0.157, 0.076) and a record-high external quantum efficiency (EQE) of 20.35% at high luminance (5000 cd m-2) is accomplished. Simple molecular synthesis and device fabrication of this strategy give a unique approach to realizing high-performance deep-blue electroluminescence.

Surfaces Decorated with Enantiomorphically Pure Polymer Nanohelices via Hierarchical Chirality Transfer across Multiple Length Scales.

Mesoscale chiral materials are prepared by lithographic methods, assembly of chiral building blocks, and through syntheses in the presence of polarized light. Typically, these processes result in micrometer-sized structures, require complex top-down manipulation, or rely on tedious asymmetric separation. Chemical vapor deposition (CVD) polymerization of chiral precursors into supported films of liquid crystals (LCs) are discovered to result in superhierarchical arrangements of enantiomorphically pure nanofibers. Depending on the molecular chirality of the 1-hydroxyethyl [2.2]paracyclophane precursor, extended arrays of enantiomorphic nanohelices are formed from achiral nematic templates. Arrays of chiral nanohelices extend over hundreds of micrometers and consistently display enantiomorphic micropatterns. The pitch of individual nanohelices depends on the enantiomeric excess and the purity of the chiral precursor, consistent with the theoretical model of a doubly twisted LC director configuration. During CVD of chiral precursors into cholesteric LC films, aspects of molecular and mesoscale asymmetry combine constructively to form regularly twisted nanohelices. Enantiomorphic surfaces permit the tailoring of a wide range of functional properties, such as the asymmetric induction of weak chiral systems.

Fluorescence detected circular dichroism (FDCD) for supramolecular host-guest complexes.

Fluorescence-detected circular dichroism (FDCD) spectroscopy is applied for the first time to supramolecular host-guest and host-protein systems and compared to the more known electronic circular dichroism (ECD). We find that FDCD can be an excellent choice for common supramolecular applications, e.g. for the detection and chirality sensing of chiral organic analytes, as well as for reaction monitoring. Our comprehensive investigations demonstrate that FDCD can be conducted in favorable circumstances at much lower concentrations than ECD measurements, even in chromophoric and auto-emissive biofluids such as blood serum, overcoming the sensitivity limitation of absorbance-based chiroptical spectroscopy. Besides, the combined use of FDCD and ECD can provide additional valuable information about the system, e.g. the chemical identity of an analyte or hidden aggregation phenomena. We believe that simultaneous FDCD- and ECD-based chiroptical characterization of emissive supramolecular systems will be of general benefit for characterizing fluorescent, chiral supramolecular systems due to the higher information content obtained by their combined use.

Molecular Design and Synthesis of Dicarbazolophane-Based Centrosymmetric Through-Space Donors for Solution-Processed Thermally Activated Delayed Fluorescence OLEDs.

Conjugation-extended carbazolophane donors, dicarbazolophanes (DCzp), were designed and synthesized using a multifold stepwise Pd-catalyzed Buchwald-Hartwig amination/ring cyclization process. Furthermore, elaboration of the DCzp core is possible with the introduction of pendant carbazole derivative groups. This provides a way to tune the optoelectronic properties of the thermally activated delayed fluorescence (TADF) compounds DCzpTRZtBu, dtBuCzDCzpTRZtBu, and dMeOCzDCzpTRZtBu. Solution-processed organic light-emitting diodes (OLEDs) were fabricated and achieved a maximum external quantum efficiency (EQEmax) of 8.2% and an EQE of 7.9% at 100 cd/m2.

OBO-Fused Benzo[fg]tetracene as Acceptor With Potential for Thermally Activated Delayed Fluorescence Emitters.

Six luminophores bearing an OBO-fused benzo[fg]tetracene core as an electron acceptor were designed and synthesized. The molecular structures of three molecules (PXZ-OBO, 5PXZ-OBO, 5DMAC-OBO) were determined by single crystal X-ray diffraction studies and revealed significant torsion between the donor moieties and the OBO acceptor with dihedral angles between 75.5 and 86.2°. Photophysical studies demonstrate that blue and deep blue emission can be realized with photoluminescence maxima (λPL) ranging from 415 to 480 nm in mCP films. The emission energy is modulated by simply varying the strength of the donor heterocycle, the number of donors, and their position relative to the acceptor. Although the DMAC derivatives show negligible delayed emission because of their large singlet-triplet excited state energy difference, ΔE ST, PXZ-based molecules, especially PXZ-OBO with an experimental ΔE ST of 0.25 eV, demonstrate delayed emission in blend mCP films at room temperature, which suggests triplet exciton harvesting occurs in these samples, potentially by thermally activated delayed fluorescence.

Rational design and implementation of a cucurbit[8]uril-based indicator-displacement assay for application in blood serum.

In this study, we report the first supramolecular indicator-displacement assay (IDA) based on cucurbit[n]uril (CBn) hosts that is operational in blood serum. Rational design principles for host-guest chemosensing in competitively binding media were derived through detailed mathematical simulations. It was shown that currently known CBn-based chemosensing ensembles are not suited for use in highly competitive matrices such as blood serum. Conversely, the simulations indicated that a combination of cucurbit[8]uril (CB8) and an ultra-high affinity dye would be a promising IDA reporter pair for the detection of Alzheimer's drug memantine in blood serum. Therefore, a novel class of [2.2]paracyclophane-derived indicator dyes for the host CB8 was developed that possesses one of the highest host-guest affinities (K a > 1012 M-1 in water) known in supramolecular host-guest chemistry, and which provides a large Stokes shift (up to 200 nm). The novel IDA was then tested for the detection of memantine in blood serum in a physiologically relevant sub- to low micromolar concentration range.

Turn on of sky-blue thermally activated delayed fluorescence and circularly polarized luminescence (CPL) via increased torsion by a bulky carbazolophane donor.

The carbazolophane (Czp) donor unit (indolo[2.2]paracyclophane) is introduced to the design pool of donors in thermally activated delayed fluorescence emitters. The increased steric bulk of the annelated donor unit forces an increased torsion between the carbazole and the aryl bridge resulting in a decreased ΔE ST and an enhancement of the thermally activated delayed fluorescence in the triazine-containing emitter CzpPhTrz. Further, the closely stacked carbazole and benzene units of the paracyclophane show through-space π-π interactions, effectively increasing the spatial occupation for the HOMO orbital. The chiroptical properties of enantiomers of [2.2]paracyclophane reveal mirror image circular dichroism (CD) and circularly polarized luminescence (CPL) with g lum of 1.3 × 10-3. rac-CzpPhTrz is a sky-blue emitter with λ PL of 480 nm, a very small ΔE ST of 0.16 eV and high Φ PL of 70% in 10 wt% doped DPEPO films. Sky blue-emitting OLEDs were fabricated with this new TADF emitter showing a high maximum EQE of 17% with CIE coordinates of (0.17, 0.25). A moderate EQE roll-off was also observed with an EQE of 12% at a display relevant luminance of 100 cd m-2. Our results show that the Czp donor contributes to both a decreased ΔE ST and an increased photoluminescence quantum yield, both advantageous in the molecular design of TADF emitters.

(Deep) blue through-space conjugated TADF emitters based on [2.2]paracyclophanes.

The first examples of through-space conjugated thermally activated delayed fluorescence (TADF) emitters based on a [2.2]paracyclophane (PCP) skeleton with stacked (coplanar) donor-acceptor groups have been synthesized. The optoelectronic properties are studied by the relative configuration, cis (pseudo-geminal) and trans (pseudo-para), of the donor and acceptor groups.