Interpenetrated Donor-Acceptor Heterojunctions in 2D Conjugated Dibenzo[g,p]chrysene-Based Kagome Covalent Organic Frameworks.

Dibenzo[g,p]chrysene can be viewed as a constrained propeller-shaped tetraphenylethylene with reduced curvature and has been utilized to construct dual-pore kagome covalent organic frameworks (COFs) with tightly packed two-dimensional (2D) layers owing to its rigid and more planar structural characteristics. Here, we introduce 2D COFs based on the node 4,4',4″,4‴-(dibenzo[g,p]chrysene-2,7,10,15-tetraphenyl)tetraamine (DBCTPTA) featuring extended conjugation compared to the dibenzo[g,p]chrysene-3,6,11,14-tetraamine (DBCTA) node. We establish two exceptionally crystalline imine-linked 2D COFs with a hexagonal dual-pore kagome structure based on the DBCTPTA core. The newly synthesized thienothiophene (TT) and benzodithiophene (BDT)-based DBCTPTA COFs show a tight stacking behavior between adjacent layers. Furthermore, we obtained an unprecedented, interpenetrated electron-donor/acceptor host-guest system with an electron-donating BDT DBCTPTA COF synthesized in situ with the soluble fullerene derivative [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) serving as molecular acceptor. The BDT DBCTPTA COF@PCBM film shows a much shorter amplitude-averaged PL lifetime of 7 ± 2 ps compared to 30 ± 4 ps of the BDT DBCTPTA COF film, indicating the light-induced charge transfer process. The successful in situ formation of interpenetrated donor-acceptor heterojunctions within 2D COFs offers a promising strategy for establishing D-A heterojunctions in diverse framework materials with open channel systems.

3D Conjugated Hole Transporting Materials for Efficient and Stable Perovskite Solar Cells and Modules.

The orthogonal structure of the widely used hole transporting material (HTM) 2,2',7,7'-tetrakis(N, N-di-p-methoxyphenylamino)-9,9'-spirobifluorene (Spiro-OMeTAD) imparts isotropic conductivity and excellent film-forming capability. However, inherently weak intra- and inter-molecular π-π interactions result in low intrinsic hole mobility. Herein, a novel HTM, termed FTPE-ST, with a twist conjugated dibenzo(g,p)chrysene core and coplanar 3,4-ethylenedioxythiophene (EDOT) as extended donor units, is designed to enhance π-π interactions, without compromising on solubility. The three-dimensional (3D) configuration provides the material multi-direction charge transport as well as excellent solubility even in 2-methylanisole, and its large conjugated backbone endows the HTM with a high hole mobility. Moreover, the sulfur donors in EDOT units coordinate with lead ions on the perovskite surface, leading to stronger interfacial interactions and the suppression of defects at the perovskite/HTM interface. As a result, perovskite solar cells (PSCs) employing FTPE-ST achieve a champion power conversion efficiency (PCE) of 25.21% with excellent long-time stability, one of the highest PCEs for non-spiro HTMs in n-i-p PSCs. In addition, the excellent film-forming capacity of the HTM enables the fabrication of FTPE-ST-based large-scale PSCs (1.0 cm2) and modules (29.0 cm2), which achieve PCEs of 24.21% (certificated 24.17%) and 21.27%, respectively.

Rational design of triazine-based conjugated polymers with enhanced charge separation ability for photocatalytic hydrogen evolution.

Triazine-based conjugated polymers (TCPs) are promising organic catalysts for green H2 production, since their photocatalytic performance can be easily regulated via appropriate molecular design. However, apart from weak absorption of visible light, weak charge separation and transport abilities also considerably restrict the photocatalytic performance of TCPs. Herein, we report two novel TCP photocatalysts with donor-acceptor (D-A) and donor-π-acceptor (D-π-A) structures using dibenzo[g,p]chrysene (Dc), thiophene (T), and 2,4,6-triphenyl-1,3,5-triazine (Tz) as the donor, π-spacer, and acceptor, respectively. Compared to Dc-Tz with a D-A structure, Dc-T-Tz exhibits a broader light absorption edge and more efficient charge separation and transmission due to its D-π-A structure and strong dipole effect. These properties enable Dc-T-Tz to display a prominent H2 production rate of 45.13 mmol h-1 g-1 under ultraviolet-visible (UV-Vis) light (λ > 300 nm). Therefore, Dc-T-Tz represents state-of-the-art TCP photocatalysts to date.

Design and Synthesis of Bisulfone-Linked Two-Dimensional Conjugated Microporous Polymers for CO2 Adsorption and Energy Storage.

We have successfully synthesized two types of two-dimensional conjugated microporous polymers (CMPs), Py-BSU and TBN-BSU CMPs, by using the Sonogashira cross-coupling reaction of BSU-Br2 (2,8-Dibromothianthrene-5,5',10,10'-Tetraoxide) with Py-T (1,3,6,8-Tetraethynylpyrene) and TBN-T (2,7,10,15-Tetraethynyldibenzo[g,p]chrysene), respectively. We characterized the chemical structure, morphology, physical properties, and potential applications of these materials using various analytical instruments. Both Py-BSU and TBN-BSU CMPs showed high thermal stability with thermal decomposition temperatures (Td10) up to 371 °C and char yields close to 48 wt%, as determined by thermogravimetric analysis (TGA). TBN-BSU CMPs exhibited a higher specific surface area and porosity of 391 m2 g-1 and 0.30 cm3 g-1, respectively, due to their large micropore and mesopore structure. These CMPs with extended π-conjugated frameworks and high surface areas are promising organic electroactive materials that can be used as electrode materials for supercapacitors (SCs) and gas adsorption. Our experimental results demonstrated that the TBN-BSU CMP electrode had better electrochemical characteristics with a longer discharge time course and a specific capacitance of 70 F g-1. Additionally, the electrode exhibited an excellent capacitance retention rate of 99.9% in the 2000-cycle stability test. The CO2 uptake capacity of TBN-BSU CMP and Py-BSU CMP were 1.60 and 1.45 mmol g-1, respectively, at 298 K and 1 bar. These results indicate that the BSU-based CMPs synthesized in this study have potential applications in electrical testing and CO2 capture.

An Efficient Electron Donor for Conjugated Microporous Polymer Photocatalysts with High Photocatalytic Hydrogen Evolution Activity.

Conjugated microporous polymers (CMPs) with donor-acceptor (D-A) molecular structure show high photocatalytic activity for hydrogen evolution due to the efficient light-induced electron/hole separation, which is mostly determined by the nature of electron donor and acceptor units. Therefore, the selection of electron donor and acceptor holds the key point to construct high performance polymer photocatalysts. Herein, two dibenzo[b,d]thiophene-S,S-dioxide (BTDO) containing CMP photocatalysts using tetraphenylethylene (TPE) or dibenzo[g,p]chrysene (DBC) as the electron donor to investigate the influence of the geometry of electron donor on the photocatalytic activity are design and synthesized. Compared with the twisted TPE donor, DBC has a planar molecular structure with extended π-conjugation, which promotes the charges transmission and light-induced electron/hole separation. As a result, the polymer DBC-BTDO produced from DBC donor shows a remarkable photocatalytic hydrogen evolution rate (HER) of 104.86 mmol h-1  g-1 under full arc light (λ > 300 nm), which is much higher than that of the polymer TPE-BTDO (1.80 mmol h-1  g-1 ), demonstrating that DBC can be an efficient electron donor for constructing D-A polymer photocatalysts with high photocatalytic activity for hydrogen evolution.

Tetraphenylethylene-Arylamine Derivatives as Hole Transporting Materials for Perovskite Solar Cells.

A series of hole transporting materials (HTMs) with fused tetraphenylethylene cores (9,9'-bifluorenylidene and dibenzo[g,p]chrysene) as well as different substitution positions of arylamine side arms has been designed and synthesized. A reference HTM with a non-fused tetraphenylethylene core is also prepared for a comparative study. It is noted that fused tetraphenylethylene molecules show a bathochromic spectral shift, electronegative character, and lower reorganization energies than the non-fused ones. Furthermore, the molecules with side arms located on the meta-position on the tetraphenylethylene core in terms of a double bond exhibit a deeper highest occupied molecular orbital level than those of the para-position-based ones whether tetraphenylethylene is fused or not. Moreover, the reorganization energies of fused meta-position-based HTMs are lower than those of para-position-based HTMs. Fused tetraphenylethylene HTMs own a better hole-extraction capability than the non-fused ones. When used in perovskite solar cells, all devices with fused tetraphenylethylene HTMs display better performance than those of the non-fused ones. The HTMs based on dibenzo[g,p]chrysene exhibit better performance than those of bifluorenylidene. Moreover, the devices with HTMs with side arms located on the meta-position on the tetraphenylethylene core display higher power conversion efficiency than those of the para-position-based ones. The results give some new insight and reference to develop ideal HTMs for perovskite solar cells.

Luminescent Tetranuclear Gold(I) Dibenzo[g,p]chrysene Derivatives: Effect of the Environment on Photophysical Properties.

A new 2,7,10,15-tetraethynyldibenzo[g,p]chrysene ligand (1) and two tetranuclear gold(I) derivatives containing PPh3 (3) and PMe3 (4) phosphines were synthesized and characterized by 1H and 31P NMR, IR spectroscopy, and high-resolution mass spectrometry. The compounds were studied in order to analyze the effect of the introduction of gold(I) on the supramolecular aggregation and photophysical properties. Absorption and emission spectra displayed broad bands due to the establishment of π π interactions as an indication of intermolecular contacts and the formation of aggregates. A decrease of the recorded quantum yield (QY) of the gold(I) derivatives was observed compared to the uncomplexed ligand. The introduction of the complexes into poly methyl methacrylate (PMMA) and Zeonex 480R matrixes was analyzed, and an increase of the measured QY of 4 in Zeonex was observed. No phosphorescent emission was detected.