Conflicting Aromaticity in Trirhodium(I) Rosarin.

Aromaticity is one of the most important and widely used concepts in chemistry. Among the various experimentally discovered and theoretically predicted compounds that possess different types of aromaticity, conflicting aromaticity, where aromatic and antiaromatic electron delocalization is present in one molecule simultaneously, remains one of the most controversial and elusive concepts, although theoretically predicted 15 years ago. In this work, we synthesized a novel conflicting aromatic trirhodium complex that contains a σ-aromatic metal fragment surrounded by the π-antiaromatic organic ligand and characterized it by nuclear magnetic resonance spectroscopy, high-resolution mass spectrometry, and X-ray single crystal structure analysis. Experimental characterization and quantum chemical calculations confirm the unique conflicting aromaticity of the synthesized trirhodium molecule. Thus, this novel conflicting aromatic molecule expands the family of aromatic compounds. This discovery will enable researchers to develop and understand the phenomena of conflicting aromaticity in chemistry.

Synthesis of π-conjugated polycyclic compounds by late-stage extrusion of chalcogen fragments.

The "precursor approach" has proved particularly valuable for the preparation of insoluble and unstable π-conjugated polycyclic compounds (π-CPCs), which cannot be synthesized via in-solution organic chemistry, for their improved processing, as well as for their electronic investigation both at the material and single-molecule scales. This method relies on the synthesis and processing of soluble and stable direct precursors of the target π-CPCs, followed by their final conversion in situ, triggered by thermal activation, photoirradiation or redox control. Beside well-established reactions involving the elimination of carbon-based small molecules, i.e., retro-Diels-Alder and decarbonylation processes, the late-stage extrusion of chalcogen fragments has emerged as a highly promising synthetic tool to access a wider variety of π-conjugated polycyclic structures and thus to expand the potentialities of the "precursor approach" for further improvements of molecular materials' performances. This review gives an overview of synthetic strategies towards π-CPCs involving the ultimate elimination of chalcogen fragments upon thermal activation, photoirradiation and electron exchange.

Complexation study of a 1,3-phenylene-bridged cyclic hexa-naphthalene with fullerenes C60 and C70 in solution and 1D-alignment of fullerenes in the crystals.

To investigate the host ability of a simple macrocycle, 1,3-phenylene-bridged naphthalene hexamer N6, we evaluated the complexation of N6 with fullerenes in toluene and in the crystals. The complexes in the solid-state demonstrate the one-dimensional alignment of fullerenes. The single-crystals of the C60@N6 composite have semiconductive properties revealed by photoconductivity measurements.

An Unsymmetrical 5,15-Disubstituted Tetrabenzoporphyrin: Effect of Molecular Symmetry on the Packing Structure and Charge Transporting Property.

Molecular design strategy to control the crystal structure of two-dimensional (2D) π-extended organic semiconductors has not been intensively explored. We synthesized an unsymmetric tetrabenzoporphyrin derivative (TIPS-Ph-BP) to demonstrate the effect of molecular symmetry on crystal packing. TIPS-Ph-BP formed an antiparallel slipped π-stacking and 2D herringbone-like structure. An unsymmetric structure would make 2D π-stacking more stable than a one-dimensional (1D) columnar structure to counteract steric and electronic imbalance in the crystal. As a result, TIPS-Ph-BP achieved the high hole mobility of 0.71 cm2 V-1 s-1.

Nonpolymer Organic Solar Cells: Microscopic Phonon Control to Suppress Nonradiative Voltage Loss via Charge-Separated State.

Recent remarkable developments on nonfullerene solar cells have reached a photoelectric conversion efficiency (PCE) of 18% by tuning the band energy levels in small molecular acceptors. In this regard, understanding the impact of small donor molecules on nonpolymer solar cells is essential. Here, we systematically investigated mechanisms of solar cell performance using diketopyrrolopyrrole (DPP)-tetrabenzoporphyrin (BP) conjugates of C4-DPP-H2BP and C4-DPP-ZnBP, where C4 represents the butyl group substituted at the DPP unit as small p-type molecules, while an acceptor of [6,6]-phenyl-C61-buthylic acid methyl ester is employed. We clarified the microscopic origins of the photocarrier caused by phonon-assisted one-dimensional (1D) electron-hole dissociations at the donor-acceptor interface. Using a time-resolved electron paramagnetic resonance, we have characterized controlled charge-recombination by manipulating disorders in π-π donor stacking. This ensures carrier transport through stacking molecular conformations to suppress nonradiative voltage loss capturing specific interfacial radical pairs separated by 1.8 nm in bulk-heterojunction solar cells. We show that, while disordered lattice motions by the π-π stackings via zinc ligation are essential to enhance the entropy for charge dissociations at the interface, too much ordered crystallinity causes the backscattering phonon to reduce the open-circuit voltage by geminate charge-recombination.

An Atropisomerism Study of Large Cycloarylenes: [n]Cyclo-4,10-Pyrenylenes' Case.

An atropisomerism of large cycloarylenes was studied using [n]cyclo-4,10-pyrenylenes (n=6-21) as an illustrative example with two simple assumptions: (1) alternating configurations (R,S,R,S,…) are thermodynamically most stable, and (2) three consecutive identical configurations (R,R,R or S,S,S) are prevented. Ni-mediated coupling of a 5,9-diiodopyrene gave a series of directly-linked cyclic pyrene oligomers in one-pot reaction. As-synthesized cyclic hexamer was assigned as an (R,S,S,R,R,S) structure, converted into an (R,S,R,S,R,S)-form upon heating. Cyclic heptamer consists of two types of C2 symmetric structures predicted from assumption (2), one of which was convergent to one another by heating. Three atropisomers of cyclic octamer were analyzed from the possible five candidates by means of 1 H nuclear magnetic resonance (NMR) spectroscopy, and the conversion process to (R,S,R,S,R,S,R,S) configurations upon heating was investigated. In total, according to two simple rules, the analysis of atropisomerism could be performed smoothly.

Diazazethrene bisimide: a strongly electron-accepting π-system synthesized via the incorporation of both imide substituents and imine-type nitrogen atoms into zethrene.

The development of highly electron-accepting π-systems is a fundamentally challenging issue despite their potential applications as high-performance n-type organic semiconductors, organic rechargeable batteries, and stable redox-active organocatalysts. Herein, we demonstrate that the incorporation of both imide substituents and imine-type nitrogen atoms into zethrene affords the strongly electron-accepting π-system diazazethrene bisimide (DAZBI). DAZBI has a low-lying LUMO (-4.3 eV vs. vacuum) and is readily reduced by the weak reductant l-ascorbic acid to afford the corresponding dihydro species. The injection of two electrons into DAZBI provides the corresponding dianion. These reduced species display remarkable stability, even under ambient conditions, and an intense red fluorescence. A DAZBI dimer, which was also synthesized, effectively accommodated four electrons upon electron injection.

Correction: Phosphaacene as a structural analogue of thienoacenes for organic semiconductors.

Correction for 'Phosphaacene as a structural analogue of thienoacenes for organic semiconductors' by Kyohei Matsuo et al., Chem. Commun., 2022, 58, 13576-13579, https://doi.org/10.1039/D2CC05122B.

Phosphaacene as a structural analogue of thienoacenes for organic semiconductors.

An air-stable λ3-phosphinine-containing polycyclic aromatic compound without steric protection was synthesized and its charge transport properties were evaluated, which revealed moderate hole mobility. This research is the first experimental demonstration of the organic electronic applications of low-coordinate phosphorus compounds.

Deep-red circularly polarised luminescent C70 derivatives.

Optically active fullerenes, including C60 and C70 derivatives carrying organic substituents, are used in a range of applications because of their unique spectroscopic, catalytic, and chiral recognition properties. However, their inherent photoexcited chirality is yet to be elucidated because of their very poor fluorescence quantum yield (Φf). We synthesised a new chiral C70 derivative, X70A, with 20% yield, by reacting bis-borylated xanthene with C70 in a one-step double addition reaction, followed by a successful optical resolution. The isolation of two separate X70A enantiomers was confirmed by mirror-image circular dichroism spectroscopy in the range of 300-750 nm. In toluene, the enantiomeric pair of X70A clearly revealed mirror-image circularly polarised luminescence (CPL) spectra with a high |glum| value of 7.0 × 10-3 at 690 nm. The first fullerene-based deep-red CPL of X70A should provide a new guideline for the design of chiral nanocarbon materials.

Synthesis and Properties of the Doubly Oxonium-Embedded Picenes as Electron-Deficient Polycyclic Aromatic Hydrocarbons.

The doubly oxonium-embedded picenes have been synthesized for the first time. They have a rigid planar electron-deficient core and are stabilized by the pyrylium aromaticity. The doping positions of oxygen atoms influenced their electrochemical and optoelectronic properties because of the different charge distributions in the skeletons. The donor-acceptor-donor-type molecules baring electron-donating triphenylamine moieties exhibited intramolecular charge-transfer absorption at the visible regions, indicating the large impact of the substituents on their electronic properties.

Acridino[2,1,9,8-klmna]acridine Bisimides: An Electron-Deficient π-System for Robust Radical Anions and n-Type Organic Semiconductors.

We report the synthesis and properties of acridino[2,1,9,8-klmna]acridine bisimide (AABI), a nitrogen-doped anthanthrene with two imide functionalities. AABI exhibits excellent electron affinity as evident by its low-lying LUMO level (-4.1 eV vs. vacuum). Single-electron reduction of one AABI derivative afforded the corresponding radical anion, which was stable under ambient conditions. Photoconductivity measurements suggest that the intrinsic electron mobility of an N-phenethyl AABI derivative obeys a band-transport model. Accordingly, an electron mobility of 0.90 cm2 V-1 s-1 was attained with the corresponding single-crystal organic field-effect transistor (OFET) device. The vacuum-deposited OFET device consisting of a polycrystalline sample exhibited high electron mobility of up to 0.27 cm2 V-1 s-1 even in air. This study demonstrates that dual incorporation of both imide substituents and imine-type nitrogen atoms is an effective strategy to create novel electron-deficient π-systems.

Dinaphthothiepine Bisimide and Its Sulfoxide: Soluble Precursors for Perylene Bisimide.

The synthesis and properties of dinaphtho[1,8-bc:1',8'-ef]thiepine bisimide (DNTBI) and its oxides are described. Their molecular design is conceptually based on the insertion of a sulfur atom into the perylene bisimide (PBI) core. These sulfur-inserted PBI derivatives adopt nonplanar structures, which significantly increases their solubility in common organic solvents. Upon electron injection, light irradiation, or heating, DNTBI and its sulfoxides undergo sulfur extrusion reactions to furnish PBI. The photoinduced and thermal sulfur extrusion reactions proceed almost quantitatively. This unique reactivity enabled the fabrication of a high-performance solution-processed n-type organic field-effect transistor with an electron mobility of up to 0.41 cm2 V-1 s-1.

Direct borylation of terrylene and quaterrylene.

The preparation of large rylenes often needs the use of solubilizing groups along the rylene backbone, and all the substituents of the terrylenes and quaterrylenes were introduced before creating the rylene skeleton. In this work, we successfully synthesized 2,5,10,13-tetrakis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)terrylene (TB4) by using an iridium-catalyzed direct borylation of C-H bonds in terrylene in 56% yield. The product is soluble in common organic solvents and could be purified without column chromatography. Single crystal X-ray diffraction analysis revealed that the terrylene core is not disturbed by the substituents and is perfectly flat. The photophysical properties of TB4 are also unchanged by the substituents because the carbon atoms at 2,5,10,13-positions have less coefficients on its HOMO and LUMO, estimated by theoretical calculations. Finally, the same borylation reaction was applied for quaterrylene, resulting in the formation of soluble tetra-borylated quaterrylene despite a low yield. The post modification of rylenes enables us to prepare their borylated products as versatile units after creating the rylene skeletons.

Boronate- and borinate-based π-systems for blue thermally activated delayed fluorescence materials.

Thermally activated delayed fluorescent molecules containing boronate-ester, -thioester, and borinate-ester moieties as electron-accepting units were designed and synthesized. OLEDs with a borinate-ester-based emitter exhibited blue electroluminescence with CIE chromaticity coordinates of (0.15, 0.15).

Blue thermally activated delayed fluorescence emitters incorporating acridan analogues with heavy group 14 elements for high-efficiency doped and non-doped OLEDs.

Deep-blue thermally activated delayed fluorescence (TADF) emitters are promising alternatives for conventional fluorescence and phosphorescence materials for practical application in organic light-emitting diodes (OLEDs). However, as appropriate bipolar hosts for deep-blue TADF-OLEDs are scarce, the development of efficient deep-blue TADF emitters that are applicable to both doped and non-doped systems is an urgent task. In this study, we developed a new family of blue TADF emitters that demonstrated high photoluminescence (PL) and electroluminescence (EL) quantum efficiencies in both doped and non-doped (neat) systems. Four new donor-acceptor (D-A)-type TADF molecules incorporating phenazasiline, phenazagermine, and tetramethylcarbazole as weak D units and phenothiaborin as a weak A unit were designed and synthesized. By varying the structural rigidity/flexibility as well as the electron-donating ability of the D units, the resulting photophysical and TADF properties of the D-A molecules could be systematically regulated. A comprehensive photophysical investigation revealed that phenazasiline and phenazagermine-based emitters concurrently exhibit blue TADF emissions (464-483 nm), high PL quantum efficiencies (∼100%), extremely fast spin-converting reverse intersystem crossing rates (>107 s-1), and suppressed concentration quenching. These fascinating features in conjunction produced high-performance doped and non-doped blue TADF-OLEDs. The doped and non-doped TADF-OLEDs using the phenazasiline-based emitter demonstrated extremely high maximum external EL quantum efficiencies (η ext) of 27.6% and 20.9%, with CIE chromaticity coordinates of (0.14, 0.26) and (0.14, 0.20), respectively. Further, ultra-low efficiency roll-off behavior for both the doped and non-doped devices was demonstrated by their η ext as high as 26.1% and 18.2%, respectively, measured at a practically high luminance of 1000 cd m-2.

Structural Monitoring of the Onset of Excited-State Aromaticity in a Liquid Crystal Phase.

Aromaticity of photoexcited molecules is an important concept in organic chemistry. Its theory, Baird's rule for triplet aromaticity since 1972 gives the rationale of photoinduced conformational changes and photochemical reactivities of cyclic π-conjugated systems. However, it is still challenging to monitor the dynamic structural change induced by the excited-state aromaticity, particularly in condensed materials. Here we report direct structural observation of a molecular motion and a subsequent packing deformation accompanied by the excited-state aromaticity. Photoactive liquid crystal (LC) molecules featuring a π-expanded cyclooctatetraene core unit are orientationally ordered but loosely packed in a columnar LC phase, and therefore a photoinduced conformational planarization by the excited-state aromaticity has been successfully observed by time-resolved electron diffractometry and vibrational spectroscopy. The structural change took place in the vicinity of excited molecules, producing a twisted stacking structure. A nanoscale torque driven by the excited-state aromaticity can be used as the working mechanism of new photoresponsive materials.

Enhancing thermally activated delayed fluorescence characteristics by intramolecular B-N coordination in a phenylpyridine-containing donor-acceptor π-system.

An efficient thermally activated delayed fluorescence emitter based on an N-heteroarene acceptor bearing an intramolecularly coordinated boryl group was developed. The impact of the B-N coordination on the optoelectronic properties and electroluminescence performance of devices was investigated.

Effects of chalcogen atom substitution on the optoelectronic and charge-transport properties in picene-type π-systems.

A series of π-conjugated 3,10-dialkyl-dinaphtho[1,2-b:2',1'-d]chalcogenophenes incorporating S, Se, and Te as the central chalcogen atom was newly synthesized, and their optoelectronic and charge-transport properties were systematically investigated. High carrier mobilities of up to 4.7 cm2 V-1 s-1 were achieved for solution-processed organic field-effect transistors using these materials as p-channel organic semiconductors.

A Soluble Dynamic Complex Strategy for the Solution-Processed Fabrication of Organic Thin-Film Transistors of a Boron-Containing Polycyclic Aromatic Hydrocarbon.

The solution-processed fabrication of thin films of organic semiconductors enables the production of cost-effective, large-area organic electronic devices under mild conditions. The formation/dissociation of a dynamic B-N coordination bond can be used for the solution-processed fabrication of semiconducting films of polycyclic aromatic hydrocarbon (PAH) materials. The poor solubility of a boron-containing PAH in chloroform, toluene, and chlorobenzene was significantly improved by addition of minor amounts (1 wt % of solvent) of pyridine derivatives, as their coordination to the boron atom suppresses the inherent propensity of the PAHs to form π-stacks. Spin-coating solutions of the thus formed Lewis acid-base complexes resulted in the formation of amorphous thin films, which could be converted into polycrystalline films of the boron-containing PAH upon thermal annealing. Organic thin-film transistors prepared by this solution process displayed typical p-type characteristics.