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An efficient strategy based on a material genome approach is created to predict highly fire-safe polycarbonates (PCs) with balanced processability. The predicted PCs show excellent comprehensive properties, especially exceptional fire-safe performance. more...

Herein, we report the synthesis and properties of a [6,6] hollow bilayer cylindrical nanoring (HBCNR) from a planar macrocycle via a Diels-Alder and Yamamoto coupling reaction. The fluorescence quantum yield of HBCNR was determined to be ΦF = 52%, which is four times higher than its precursor. In addition, its hollow nanoring configuration was also simulated by theoretical studies, and the tension energy was estimated to be 47.1 kcal/mol. more...

Carbon nanobelts (CNBs) are a new form of nanocarbon that has promising applications in optoelectronics due to their unique belt-shaped π-conjugated systems. Recent synthetic breakthrough has led to the access to various CNBs, but their optoelectronic properties have not been explored yet. In this work, we study the electronic transport performance of a series of CNBs by incorporating them into molecular devices using the scanning tunneling microscope break junction technique. We show that, by tuning the bridging groups between the adjacent benzenes in the CNBs, we can achieve remarkably high conductance close to 0.1 G 0 , nearly one order of magnitude higher than their nanoring counterpart cycloparaphenylene. Density functional theory–based calculations further elucidate the crucial role of the structural distortion played in facilitating the unique radial π-electron delocalization and charge transport across the belt-shaped carbon skeletons. These results develop a basic understanding of electronic transport properties of CNBs and lay the foundation for further exploration of CNB-based optoelectronic applications. more...

The increasing devices and their demand for network force the IoT network for smart grids to face the great challenges in privacy, security, trust, etc. In this paper, we apply blockchain to IoT communication network supported by WiFi. We first analyze the benefit that can be obtained by utilizing blockchain. And Secondly, we propose a blockchain enabled IoT network architure, within which, WAPI is applied as the authentication standard while blockchain is used as the trust guarantee mechanism. Thridly, we analyze how to guarantee the security, privacy, resource management within the proposed architecture. Finally, we conclude our work. more...

Herein, we report the synthesis, characterization, and photophysical properties of the crown-like structure of [3]cyclo-1,8-pyrenes (compounds 9 and 10). Planar pyrenyl arylene-ethynylene macrocycles are used as the precursors to synthesize these pyrene-based cycloarenes by [4 + 2] cycloaddition reaction with good yields. These molecules are confirmed by nuclear magnetic resonance spectroscopy and high-resolution mass spectrometry. The structure of 9 was unambiguously determined by single-crystal X-ray diffraction. Their photophysical properties are investigated by steady-state absorption, fluorescence, and time-resolved fluorescence spectroscopies, combined with theoretical calculations. more...

Herein, we design and synthesize a novel all-carbon supramolecular polymer host (SPh) containing conjugated macrocycles interconnected by a linear poly(para-phenylene) backbone. Applying the supramolecular host and fullerene C60 as the guest, we successfully construct a supramolecular polymeric heterojunction (SPh⊃C60). This carbon structure offers a means to explore the convex–concave π–π interactions between SPh and C60. The produced SPh was characterized by gel permeation chromatography, mass spectrometry, FTIR, Raman spectroscopy, and other spectroscopies. The polymeric segment can be directly viewed using a scanning tunneling microscope. Femtosecond transient absorption and fluorescence up-conversion measurements revealed femtosecond (≪300 fs) electron transfer from photoexcited SPh to C60, followed by nanosecond charge recombination to produce the C60 triplet excited state. The potential applications of SPh⊃C60 in electron- and hole-transport devices were also investigated, revealing that C60 incorporation enhances the charge transport properties of SPh. These results expand the scope of the synthesis and application of supramolecular polymeric heterojunctions., Herein, we design and synthesize a novel all-carbon supramolecular polymer host (SPh) containing conjugated macrocycles interconnected by a linear poly(para-phenylene) backbone. more...

Direct π-extension by the Scholl reaction for solution-based growth of armchair edges in curved macrocyclic hydrocarbon nanostructures is a great challenge. To date, several attempts at direct π-extension of small highly strained macrocycles have failed. Herein, we report a fixed two-bond approach for direct functionalization of small strained macrocyclic nanorings. The reaction occurs selectively to produce large π-extended molecular crowns with high yields. The design of these precursors features two peripheral C–C bonds that are readily incorporated into the extended aromatic moiety to overcome strain-induced side reactions, such as 1,2-phenyl shift. The crown-shaped macrocycle 10 showed a significant redshift (∼100 nm for absorption) compared with its precursor. This synthesis strategy could pave the way towards the π-extension of strained conjugated macrocycles and their potential applications in electron-transport devices. more...

The total synthesis of carbon onions is a significant challenge in the fields of materials science and organic chemistry. To date, the synthesis of even a fragment of fullerene C240 and its smallest carbon onion C60@C240 remains poorly explored. Herein, we demonstrate a bottom-up strategy to produce a novel π-extended molecular crown-shaped molecule (MC3) containing curved pentagonal and hexagonal units. This molecular crown represents a curved model compound for fullerene C240 and is fully characterized by NMR, mass spectrometry, UV-vis absorption, and from its emission spectra. Its supramolecular host–guest interaction with fullerene C60 is also investigated. MC3 and C60@MC3 can potentially be employed as seeds or templates for the bottom-up synthesis of fullerene C240 and the carbon onion C60@C240, respectively. more...

Distorting linear polyaromatic hydrocarbons (PAHs) out of planarity affects their physical properties and breaks their symmetry to induce inherent chirality. However, the chirality cannot be achieved in large distorted PAHs-based macrocycles due to a low racemization barrier for isomerization. Herein, we report the precise synthesis and tuning size-dependent (chir)optical properties of a new class of chiral PAHs-containing conjugated macrocycles (cyclo[n]paraphenylene-2,6-anthrylene, [n]CPPAn more...

ConspectusDesigning and synthesizing topologically unique molecules is a long-term challenge for synthetic chemists. Classical polycyclic aromatic hydrocarbons (PAHs) are a large group of π-conjugated planar organic compounds with rich photophysical and electronic properties, while nonplanar/curved PAHs have different molecular orbital arrangements and demonstrate unique properties. The chemistry of curved aromatic molecules has been of significant interest to explore the relationship between π conjugation and molecular geometry, which offers an attractive combination of fundamental problems, potential applications, and aesthetic appeal. Remarkable advances have been made in the last few decades during the discovery of novel curved aromatic molecules, including corannulenes, fullerenes, and carbon nanotubes (CNTs). Especially, there has been increasing interest in making single-chirality CNTs and their curved molecular components (known as finite segments of CNTs) with a fixed geometry. The most representative examples of such organic molecules are cycloparaphenylenes (CPPs) and related carbon nanorings, which possess cylindrical topologies and nanoscale conjugated segments similar to CNTs. CPPs, as the shortest cross-section and the simplest structure of armchair CNTs, have been synthetically accessible since 2008. Recent years have witnessed breakthroughs and rapid development in the synthesis of CPP-based nanorings as well as their derived molecules. In these molecules, the distortion from aromatic planarity can induce radially oriented π systems and further affect their electronic, optical, self-assembly, and charge-transport characteristics. These unique and interesting carbon nanorings are potentially useful in a variety of optoelectronic and biomedical materials. It is well-known that extension of the π-conjugated system facilitates the delocalization of π electrons and the redistribution of electronic clouds, leading to rich diversification of physical properties in the fields of electronics, optics, and supramolecular chemistry. Therefore, the precise design and controllable synthesis of carbon nanorings with large π conjugation will promote important advances in synthetic chemistry. To date, a number of π-extended carbon nanorings have been reported, and they exhibit novel physicochemical properties resulting from their fascinating topologies and structures. However, challenges still remain in the synthesis of π-extended carbon nanorings and their structural analogues and exploration of their unique properties.In this Account, we give a brief overview of our efforts to synthesize large π-extended carbon nanorings using different strategies and explore their novel applications. In 2013 we started our research on the synthesis of carbon nanorings with large π-conjugated structures. This research project has led to (i) the successful preparation of a series of carbon nanorings with inserted PAHs, especially with various nanographenes inserted, such as hexa-peri-hexabenzocoronene; (ii) the design and synthesis of a series of carbon nanorings consisting solely of PAHs; and (iii) the initial synthesis of π-extended carbon-nanoring-based polymers as the long polymeric segments of CNTs, in which macrocyclic CPPs as the basic repeating blocks were covalently coupled together. Herein we describe in detail how these challenging π-extended carbon nanorings were synthesized, and their interesting physical properties are discussed. more...

Herein, we report the synthesis of a novel porous polymer, PS2, containing radially π-conjugated carbocycles and a linear phenylene backbone. The PS2-based membrane has a distinct small size cutoff (ca. 2.6 nm) and a major size at ∼1.5 nm for the size-selective separation of nanoparticles. more...

Conjugated polymers have attracted much attention for many years and have applications in various organic devices. Carbon nanotubes can be considered as all-carbon tube-shaped conjugated polymers c... more...

Direct π-extension by the Scholl reaction for solution-based growth of armchair edges in curved macrocyclic hydrocarbon nanostructures is a great challenge. To date, several attempts at direct π-extension of small highly strained macrocycles have failed. Herein, we report a fixed two-bond approach for direct functionalization of small strained macrocyclic nanorings. The reaction occurs selectively to produce large π-extended molecular crowns with high yields. The design of these precursors features two peripheral C-C bonds that are readily incorporated into the extended aromatic moiety to overcome strain-induced side reactions, such as 1,2-phenyl shift. The crown-shaped macrocycle more...

Herein, we report the precise synthesis of a 3D highly strained all-phenylene bismacrocycle, termed conjoined (1,4)[10]cycloparaphenylenophane (SCPP[10]). This structure consists of a twisted benzene ring which is bridged twice by phenylene units anchored in two para-positions. The conjoined structure of SCPP[10] was confirmed in real space at the atomic scale by scanning tunneling microscopy. Theoretical calculations indicate that this bismacrocycle has a very high strain energy of 110.59 kcal mol-1 and the largest interphenylene torsion angle of 46.07° caused by multiple repulsive interactions. Furthermore, a 1:2 host-guest complex of SCPP[10] and [6,6]-phenyl-C61 -butyric acid methyl ester was investigated, which represents the first peanut-shaped 1:2 host-guest complex based on bismacrocycles. more...

The physical properties of conjugated cycloparaphenylene-based materials highly depend on their sizes, geometries, and functional groups. Herein we reported a facile strategy to synthesize novel multifunctionalized octamethoxy-[8]cycloparaphenylene (OMe-[8]CPP). Remarkably, an unusual hypsochromic shift in the emission spectrum was observed compared to its unfunctionalized nanoring. In addition, the photoinduced electron transfer process between OMe-[8]CPP and a naphthalene diimide electron acceptor is studied for the first time. OMe-[8]CPP will provide a suitable platform for subsequent synthesis manipulations to construct interesting and unprecedented functional nanocarbon structures. more...

Organic solar cells are an interesting and promising photovoltaic technology which has faced a strong development in the last decade. Still, there is plenty of room for device improvement. Many different parameters, not always easy to control, determine the final power conversion efficiency. In this work we analyze the impact of unbalance charge carrier mobilities. It is known that a different charge mobility for electrons and holes determines a reduction in performance. We have developed a numerical model that includes the 3D morphology of the blend in the simulator. With this model we are able to observe the charge and current density distribution across the blend at different working points. We have investigated the effect of charge unbalance to solar cell performance. more...