Sp2-carbon-conjugated covalent organic frameworks (sp2c-COFs) have emerged as promising platforms for phototo–chemical energy conversion due to their tailorable optoelectronic properties, in-plane ...π-conjugations, and robust structures. However, the development of sp2c-COFs in photocatalysis is still highly hindered by their limited linkage chemistry. Herein, we report a novel thiadiazole-bridged sp2c-COF (sp2c-COF-ST) synthesized by thiadiazole-mediated aldol-type polycondensation. The resultant sp2c-COF-ST demonstrates high chemical stability under strong acids and bases (12 M HCl or 12 M NaOH). The electro-deficient thiadiazole together with fully conjugated and planar skeleton endows sp2c-COF-ST with superior photoelectrochemical performance and charge-carrier separation and migration ability. As a result, when employed as a photocathode, sp2c-COF-ST exhibits a significant photocurrent up to ∼14.5 μA cm–2 at 0.3 V vs reversible hydrogen electrode (RHE) under visible-light irradiation (>420 nm), which is much higher than those analogous COFs with partial imine linkages (mix-COF-SNT ∼ 9.5 μA cm–2) and full imine linkages (imi-COF-SNNT ∼ 4.9 μA cm–2), emphasizing the importance of the structure–property relationships. Further temperature-dependent photoluminescence spectra and density functional theory calculations demonstrate that the sp2c-COF-ST has smaller exciton binding energy as well as effective mass in comparison to mix-COF-SNT and imi-COF-SNNT, which suggests that the sp2c-conjugated skeleton enhances the exciton dissociation and carrier migration under light irradiation. This work highlights the design and preparation of thiadiazole-bridged sp2c-COFs with promising photocatalytic performance.
Vinylene/olefin-linked two-dimensional covalent organic frameworks (v-2D-COFs), featured with vinylene-linked in-plane conjugations, high chemical stabilities, and designable chemical structures, are ...promising for optoelectronic/photocatalytic applications. Developing v-2D-COFs with superior π-conjugation and optoelectronic properties is meaningful but remains challenging. In this work, we present the crystalline benzobisthiazole-bridged unsubstituted v-2D-COF (v-2D-COF-NS1 and v-2D-COF-NS2) synthesized via a benzothiazole-mediated aldol-type polycondensation. Interestingly, the resultant v-2D-COF exhibits a high chemical stability under both strong acidic (12 M HCl) and basic conditions (saturated KOH) due to the robust vinylene-linked skeletons. Moreover, the electron-deficient thiazole units and 2D π-conjugations endow v-2D-COFs (i.e., v-2D-COF-NS1) a narrow band gap of ∼1.85 eV with a conduction band of −3.65 eV vs vacuum, which are desirable for photocatalytic hydrogen evolution. As such, the v-2D-COF-NS1-based photoelectrode gives a photocurrent up to ∼47 μA cm–2 at 0.3 V vs reversible hydrogen electrode (RHE), which is much higher than the value of the corresponding linear polymer (LP-NS1) and outstanding among the reported COF photoelectrodes. Under a continuous visible light irradiation, v-2D-COF-NS1 generates hydrogen gas with an excellent rate of ∼4.4 mmol h–1 g–1 over 12 h. This work demonstrates the synthesis of unsubstituted v-2D-COFs that intrinsically contain benzobisthiazole-based building blocks and shows great potential in photocatalytic reactions.
Abstract
Optically switchable field‐effect transistors (OSFETs) are non‐volatile photonic memory devices holding a great potential for applications in optical information storage and ...telecommunications. Solution processing of blends of photochromic molecules and π‐conjugated polymers is a low‐cost protocol to integrate simultaneously optical switching and charge transport functions in large‐area devices. However, the limited reversibility of the isomerization of photochromic molecules due to steric hindrance when embedded in ordered polymeric matrices represents a severe limitation and it obliges to incorporate as much as 20% in weight of the photochromic component, thereby drastically diluting the electronic function, limiting the device performance. Herein, a comparative study of the photoresponsivity of a suitably designed diarylethene molecule is reported when embedded in the matrix of six different polymer semiconductors displaying diverse charge transport properties. In particular, this study focuses on three semi‐crystalline polymers and three quasi‐1D polymers. It is found that 1% w/w of 1,2‐bis(5‐(3,5‐di‐tert‐butylphenyl)‐2‐methylthiophen‐3‐yl)cyclopent‐1‐ene in a blend with poly(indacenodithiophene‐co‐benzothiadiazole) is sufficient to fabricate OSFETs combining photo‐modulation efficiencies of 45.5%, mobilities >1 cm
2
V
−1
s
−1
, and photo‐recovered efficiencies of 98.1%. These findings demonstrate that quasi‐1D polymer semiconductors, because of their charge transport dominated by intra‐molecular processes, epitomize the molecular design principles required for the fabrication of high‐performance OSFETs.
Abstract Na metal batteries are regarded as an encouraging route for energy‐dense and low‐cost battery systems. However, the unstable and irreversible Na plating/stripping, caused by the uncontrolled ...dendritic Na growth, prevents their practical applications. Herein, a two‐dimensional sp 2 ‐carbon‐linked covalent organic framework (cyano‐sp 2 c‐COF) is adopted as seeding/hosting coating layer for a highly stable interface with long cycling life, large capacity, and high Na utilization. Benefit from the features of a fully π‐conjugated structure and well‐defined cyano groups, cyano‐sp 2 c‐COF with superior sodiophilicity and small interface resistance can reduce the nucleation barrier, enable Na ion flux uniformity, and enhance interface stability. Ultimately, the system achieves a low nucleation overpotential of only 10 mV, a remarkable average Coulombic efficiency of 99.7% maintained over 500 cycles in half cells, and exceptional interfacial durability of 8500 h with a high accumulated capacity of 8.5 Ah cm −2 in symmetric cells. Furthermore, the symmetric cells also present a steady cycling, even increasing the depth of discharge up to 90%. As proof, full cells demonstrate a long lifespan enduring 2700 cycles with tiny capacity decay, providing valuable insights into the long‐life Na batteries.
Persistent luminescence from triplet excitons in organic molecules is rare, as fast non‐radiative deactivation typically dominates over radiative transitions. This work demonstrates that the ...substitution of a hydrogen atom in a derivative of phenanthroimidazole with an N‐phenyl ring can substantially stabilize the excited state. This stabilization converts an organic material without phosphorescence emission into a molecular system exhibiting efficient and ultralong afterglow phosphorescence at room temperature. Results from systematic photophysical investigations, kinetic modeling, excited‐state dynamic modeling, and single‐crystal structure analysis identify that the long‐lived triplets originate from a reduction of intrinsic non‐radiative molecular relaxations. Further modification of the N‐phenyl ring with halogen atoms affects the afterglow lifetime and quantum yield. As a proof‐of‐concept, an anticounterfeiting device is demonstrated with a time‐dependent Morse code feature for data encryption based on these emitters. A fundamental design principle is outlined to achieve long‐lived and emissive triplet states by suppressing intrinsic non‐radiative relaxations in the form of molecular vibrations or rotations.
The substitution of a hydrogen atom with an N‐phenyl ring is demonstrated to convert an organic material without phosphorescence emission into a molecular system exhibiting efficient and ultralong afterglow phosphorescence at room temperature, originating from a reduction of intrinsic non‐radiative molecular relaxations, which can be used for data safety applications.
Sp
-carbon-conjugated covalent organic frameworks (sp
c-COFs) have emerged as promising platforms for phototo-chemical energy conversion due to their tailorable optoelectronic properties, in-plane ...π-conjugations, and robust structures. However, the development of sp
c-COFs in photocatalysis is still highly hindered by their limited linkage chemistry. Herein, we report a novel thiadiazole-bridged sp
c-COF (sp
c-COF-ST) synthesized by thiadiazole-mediated aldol-type polycondensation. The resultant sp
c-COF-ST demonstrates high chemical stability under strong acids and bases (12 M HCl or 12 M NaOH). The electro-deficient thiadiazole together with fully conjugated and planar skeleton endows sp
c-COF-ST with superior photoelectrochemical performance and charge-carrier separation and migration ability. As a result, when employed as a photocathode, sp
c-COF-ST exhibits a significant photocurrent up to ∼14.5 μA cm
at 0.3 V vs reversible hydrogen electrode (RHE) under visible-light irradiation (>420 nm), which is much higher than those analogous COFs with partial imine linkages (mix-COF-SNT ∼ 9.5 μA cm
) and full imine linkages (imi-COF-SNNT ∼ 4.9 μA cm
), emphasizing the importance of the structure-property relationships. Further temperature-dependent photoluminescence spectra and density functional theory calculations demonstrate that the sp
c-COF-ST has smaller exciton binding energy as well as effective mass in comparison to mix-COF-SNT and imi-COF-SNNT, which suggests that the sp
c-conjugated skeleton enhances the exciton dissociation and carrier migration under light irradiation. This work highlights the design and preparation of thiadiazole-bridged sp
c-COFs with promising photocatalytic performance.
Vinylene‐linked two‐dimensional conjugated covalent organic frameworks (V‐2D‐COFs), belonging to the class of two‐dimensional conjugated polymers, have attracted increasing attention due to their ...extended π‐conjugation over the 2D backbones associated with high chemical stability. The Knoevenagel polycondensation has been demonstrated as a robust synthetic method to provide cyano (CN)‐substituted V‐2D‐COFs with unique optoelectronic, magnetic, and redox properties. Despite the successful synthesis, it remains elusive for the relevant polymerization mechanism, which leads to relatively low crystallinity and poor reproducibility. In this work, we demonstrate the novel synthesis of CN‐substituted V‐2D‐COFs via the combination of Knoevenagel polycondensation and water‐assisted dynamic Michael‐addition‐elimination, abbreviated as KMAE polymerization. The existence of C=C bond exchange between two diphenylacrylonitriles (M1 and M6) is firstly confirmed via in situ high‐temperature NMR spectroscopy study of model reactions. Notably, the intermediate M4 synthesized via Michael‐addition can proceed the Michael‐elimination quantitatively, leading to an efficient C=C bond exchange, unambiguously confirming the dynamic nature of Michael‐addition‐elimination. Furthermore, the addition of water can significantly promote the reaction rate of Michael‐addition‐elimination for highly efficient C=C bond exchange within 5 mins. As a result, the KMAE polymerization provides a highly efficient strategy for the synthesis of CN‐substituted V‐2D‐COFs with high crystallinity, as demonstrated by four examples of V‐2D‐COF‐TFPB‐PDAN, V‐2D‐COF‐TFPT‐PDAN, V‐2D‐COF‐TFPB‐BDAN, and V‐2D‐COF‐HATN‐BDAN, based on the simulated and experimental powder X‐ray diffraction (PXRD) patterns as well as N2‐adsorption–desorption measurements. Moreover, high‐resolution transmission electron microscopy (HR‐TEM) analysis shows crystalline domain sizes ranging from 20 to 100 nm for the newly synthesized V‐2D‐COFs.
Synthesis of vinylene‐linked 2D COFs via Knoevenagel polycondensation and in situ water‐assisted Michael‐addition‐elimination: The addition of water can accelerate the Michael‐addition‐elimination for C=C bond exchange.
Linear conjugated polymers have attracted significant attention in organic electronics in recent decades. However, despite intrachain π‐delocalization, interchain hopping is their transport ...bottleneck. In contrast, two‐dimensional (2D) conjugated polymers, as represented by 2D π‐conjugated covalent organic frameworks (2D c‐COFs), can provide multiple conjugated strands to enhance the delocalization of charge carriers in space. Herein, we demonstrate the first example of thiophene‐based 2D poly(arylene vinylene)s (PAVs, 2DPAV‐BDT‐BT and 2DPAV‐BDT‐BP, BDT=benzodithiophene, BT=bithiophene, BP=biphenyl) via Knoevenagel polycondensation. Compared with 2DPAV‐BDT‐BP, the fully thiophene‐based 2DPAV‐BDT‐BT exhibits enhanced planarity and π‐delocalization with a small band gap (1.62 eV) and large electronic band dispersion, as revealed by the optical absorption and density functional calculations. Remarkably, temperature‐dependent terahertz spectroscopy discloses a unique band‐like transport and outstanding room‐temperature charge mobility for 2DPAV‐BDT‐BT (65 cm2 V−1 s−1), which far exceeds that of the linear PAVs, 2DPAV‐BDT‐BP, and the reported 2D c‐COFs in the powder form. This work highlights the great potential of thiophene‐based 2D PAVs as candidates for high‐performance opto‐electronics.
Crystalline, planar and fully thiophene‐based two‐dimensional poly(arylene vinylene) is developed for the first time via Knoevenagel polycondensation. It exhibits a narrow optical band gap and efficient π‐delocalization for band‐like transport and high charge carrier mobility.
Perfluorooctanoic acid (PFOA) is an environmental contaminant ubiquitous in water resources, which as a xenobiotic and carcinogenic agent, severely endangers human health. The development of ...techniques for its efficient removal is therefore highly sought after. Herein, we demonstrate an unprecedented zirconium-based MOF (PCN-999) possessing Zr6 and biformate-bridged (Zr6)2 clusters simultaneously, which exhibits an exceptional PFOA uptake of 1089 mg/g (2.63 mmol/g), representing a ca. 50% increase over the previous record for MOFs. Single-crystal X-ray diffraction studies and computational analysis revealed that the (Zr6)2 clusters offer additional open coordination sites for hosting PFOA. The coordinated PFOAs further enhance the interaction between coordinated and free PFOAs for physical adsorption, boosting the adsorption capacity to an unparalleled high standard. Our findings represent a major step forward in the fundamental understanding of the MOF-based PFOA removal mechanism, paving the way toward the rational design of next-generation adsorbents for per- and polyfluoroalkyl substance (PFAS) removal.
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