Helicenes have attracted considerable attention due to their inherent helical chirality and extended π-conjugation. Recently, rapid progress has been witnessed in the preparation of double, triple, quadruple, quintuple, and sextuple helicenes, where plural helicene moieties are symmetrically arranged in a single molecule. While synthetic efforts and X-ray crystallographic analyses devoted to these multiple helicenes and theoretical investigations on their isomerization and racemization behaviors have been relatively well documented and reviewed in the literature, the chiroptical properties of the multiple helicities have been somewhat overlooked. This review discourses the cumulative and systematic investigations on the chiroptical properties such as the circular dichroism (CD) and circularly polarized luminescence (CPL) of multiple helicenes. Although the number and structural variations of multiple helicenes reported to date have been fairly limited, this review overviews the current status of the chemistry of multiple helicenes from the viewpoint of chiroptical properties and provides insights into the design principle for advanced chiroptical materials through the proper arrangement of multiple helices, highlighting the impact of the molecular symmetry on the chiroptical responses.

Chiroptical Properties of Symmetric Double, Triple, and Multiple Helicenes.

The development of helicene molecules with significant chiroptical responses covering a broad range of the visible spectrum is highly desirable for chiral optoelectronic applications; however, their absorption dissymmetry factors (gabs) have been mostly lower than 0.01. In this work, we report unprecedented B,N-embedded double hetero[7]helicenes with nonbonded B and N atoms, which exhibit excellent chiroptical properties, such as strong chiroptical activities from 300 to 700 nm, record high gabs up to 0.033 in the visible spectral range, and tunable circularly polarized luminescence (CPL) from red to near-infrared regions (600-800 nm) with high photoluminescence quantum yields (PLQYs) up to 100%. As revealed by theoretical analyses, the high gabs values are related to the separate molecular orbital distributions owing to the incorporation of nonbonded B and N atoms. The new type of B,N-embedded double heterohelicenes opens up an appealing avenue to the future exploitation of high-performance chiroptical materials.

B,N-Embedded Double Hetero[7]helicenes with Strong Chiroptical Responses in the Visible Light Region.

As cut-outs from a graphene sheet, nanographenes (NGs) and graphene nanoribbons (GNRs) are ideal cases with which to connect the world of molecules with that of bulk carbon materials. While various top-down approaches have been developed to produce such nanostructures in high yields, in the present perspective, precision structural control is emphasized for the length, width, and edge structures of NGs and GNRs achieved by modern solution and on-surface syntheses. Their structural possibilities have been further extended from “flatland” to the three-dimensional world, where chirality and handedness are the jewels in the crown. In addition to properties exhibited at the molecular level, self-assembly and thin-film structures cannot be neglected, which emphasizes the importance of processing techniques. With the rich toolkit of chemistry in hand, NGs and GNRs can be endowed with versatile properties and functions ranging from stimulated emission to spintronics and from bioimaging to energy storage, thus demonstrating their multitalents in present and future materials science.

https://pubs.acs.org/doi/pdf/10.1021/jacs.2c02491

Nanographenes and Graphene Nanoribbons as Multitalents of Present and Future Materials Science

We report a new family of hexa-peri-hexabenzocoronene (HBC)-based helical nanographenes incorporating π-extended carbo[5]helicenes bearing an octagonal carbocycle. This family represents a new kind of highly distorted saddle-helix hybrid nanographenes. For the first time, the eight-membered ring becomes a constituent of both a carbo[5]helicene and a HBC and thus, the negative curvature is responsible for twisting both units. This novel chiral motif, namely, oct-[5]helicene results in the largest torsion angle recorded so far for a carbo[5]helicene (θ=79.5°), as it has been suggested by DFT-calculations and confirmed by X-ray crystallography. Consequently, the barriers of isomerization become exceptionally high for a [5]helicene unsubstituted in the fjord region since neither racemization nor decomposition were observed at 200 °C for 1 or 3 during 5 h. Therefore, racemic resolutions allowed subsequent chiroptical studies showing the ECD and CPL responses of this novel family of chiral nanographenes.

Octagon-Embedded Carbohelicene as a Chiral Motif for Circularly Polarized Luminescence Emission of Saddle-Helix Nanographenes

The past decade has witnessed remarkable success in the synthesis of curved polycyclic aromatics through Scholl reactions which enable oxidative aryl-aryl coupling even in company with the introduction of significant steric strain. These curved polycyclic aromatics are not only unique objects of structural organic chemistry in relation to the nature of aromaticity but also play an important role in bottom-up approaches to precise synthesis of nanocarbons of unique topology. Moreover, they have received considerable attention in the fields of supramolecular chemistry and organic functional materials because of their interesting properties and promising applications. Despite the great success of Scholl reactions in synthesis of curved polycyclic aromatics, the outcome of a newly designed substrate in the Scholl reaction still cannot be predicted in a generic and precise manner largely due to limited understanding on the reaction mechanism and possible rearrangement processes. This review provides an overview of Scholl reactions with a focus on their applications in synthesis of curved polycyclic aromatics with interesting structures and properties and aims to shed light on the key factors that affect Scholl reactions in synthesizing sterically strained polycyclic aromatics.

The Scholl Reaction as a Powerful Tool for Synthesis of Curved Polycyclic Aromatics.

This work describes a synthetic chiral graphene nanoribbon, named supertwistacene 1. It has four superbenzene (HBC) units linearly fused in a helical manner. The structure of 1, 4.3 nm in length, with an end-to-end twist of 117°, was confirmed by single-crystal X-ray diffraction. In contrast to various twistacene compounds and their analogues, 1 has a very stable configuration. It resists thermal isomerization even when being heated at 200 °C for 16 h. Enantiopure 1 obtained by chiral HPLC shows distinct CD signals in a broad spectral range until 600 nm. In addition, two smaller congeners of 1, the trimer 2 and the dimer 3, were also prepared and systematically investigated. Combining theoretical and experimental studies on 1-3 presents a big picture on their (chir)optical and electronic characteristics.

Supertwistacene: A Helical Graphene Nanoribbon.

This work reports the first double π-extended undecabenzo[7]helicene 1 , which is a large chiral nanographene, composed of 65 fused rings and 186 conjugated carbon atoms. The molecular identity of 1 has been confirmed by single crystal X-ray diffraction. A wine coloured solution of 1 in dichloromethane absorbs light from ultraviolet to the near infrared, featuring an extremely large molar absorption coefficient of 844000 M -1 cm -1 at 573 nm. Optically pure 1 shows a record high electronic circular dichroism intensity in the visible spectral range (|Δe| = 1375 M -1 cm -1 at 430 nm) known for any discrete polycyclic aromatic hydrocarbon. These unusual photophysical properties of 1 contrast sharply with those of a mono-undecabenzo[7]helicene derivative 2 .

Double π-Extended Undecabenzo[7]helicene.

Porous alumina was prepared via a sacrificial template method using alumina as the matrix and starch and carbon fibers as the pore-forming agents. After sintering, no residual pore-forming agents were present. The density, porosity, and pore structure of the samples were measured using the Archimedes’ method and mercury intrusion porosimetry (MIP). The results showed that the pore size distribution of porous alumina was double-peak when the content of the pore-forming agent was 20, 30, or 50 vol.%, but was single-peak when the content was 40 vol.%. A fractal model based on the measured MIP data was used to calculate and evaluate the fractal dimension (Ds) of porous alumina. The Ds values decreased with an increase in the pore-forming agent content. Furthermore, Ds was negatively correlated with porosity, most probable pore size, and median pore diameter and positively correlated with the bending strength of porous alumina. Since porous alumina has obvious fractal characteristics, the fractal theory can be used to quantitatively describe its complex distribution.

https://www.mdpi.com/2504-3110/6/10/574/pdf?version=1666691637

Zhixing Luo

Papers

Supertwistacene: A Helical Graphene Nanoribbon.

Double π-Extended Undecabenzo[7]helicene.

Fractal Dimension Analysis of Structure and Bending Strength of Porous Alumina Prepared Using Starch and Carbon Fiber as Pore-Forming Agents