Search

The mono-base-stabilized 1,2-diboranylidenehydrazine derivatives featuring a 1,3-dipolar BNN skeleton are obtained by dehydrobromination of [ArB(Br)NH]2 (Ar = 2,6-diphenylphenyl (Dpp), Ar = 2,6-bis(2,4,6-trimethylphenyl)phenyl (Dmp) or Ar = 2,4,6-tri-tert-butylphenyl (Mes*)) with N-heterocyclic carbenes (NHCs). Depending on the Ar substituents, such species can be isolated as a crystalline solid (Ar = Mes*) or generated as reactive intermediates undergoing spontaneous intramolecular aminoboration of the proximal arene rings via [3 + 2] cycloaddition (Ar = Dpp or Dmp). The latter reactions showcase the 1,3-dipolar reactivity toward unactivated arenes at ambient temperature. In addition, double cycloaddition of the isolable BNN species with two CO2 molecules affords a bicyclic species consisting of two fused five-membered BN2CO rings. The electronic structures of these BNN species and the mechanisms of these cascade reactions are interrogated through density functional theory (DFT) calculations.

Polyhedra are ubiquitous in chemistry, biology, mathematics and other disciplines. Coordination-driven self-assembly has created molecules mimicking Platonic, Archimedean and even Goldberg polyhedra, however, nesting multiple polyhedra in one cluster is challenging, not only for synthesis but also for determining the alignment of the polyhedra. Here, we synthesize a nested Ag90 nanocluster under solvothermal condition. This pseudo-Th symmetric Ag90 ball contains three concentric Ag polyhedra with apparently incompatible symmetry. Specifically, the inner (Ag6) and middle (Ag24) shells are octahedral (Oh), an octahedron (a Platonic solid with six 3.3.3.3 vertices) and a truncated octahedron (an Archimedean solid with twenty-four 4.6.6 vertices), whereas the outer (Ag60) shell is icosahedral (Ih), a rhombicosidodecahedron (an Archimedean solid with sixty 3.4.5.4 vertices). The Ag90 nanocluster solves the apparent incompatibility with the most symmetric arrangement of 2- and 3-fold rotational axes, similar to the arrangement in the model called Kepler's Kosmos, devised by the mathematician John Conway.

Plastic pollution is worsening the living conditions on Earth, primarily due to the toxicity and stability of non‐biodegradable plastics (NBPs). Photocatalytic cracking of NBPs is emerging as a promising way to cleave inert C−C bonds and abstract the carbon atoms from these wastes into valuable chemicals and fuels. However, controlling these processes is a huge challenge, ascribed to the complicated reactions of various NBPs. Herein, we summarize recent advances in the CO2 and carbon‐radical‐mediated photocatalytic cracking of NBPs, with an emphasis on the pivotal intermediates. The CO2‐mediated cracking proceeded with indiscriminate C−H/C−C bond cleavage of NBPs and tandem photoreduction of CO2, while carbon‐radical‐mediated cracking was realized by the prior activation of C−H bonds for selective C−C bond cleavage of NBPs. Catalytic generation and conversion of different intermediates greatly depend on the kinds of active species and the structure of photocatalysts under irradiation. Meanwhile, the fate of a specific intermediate is compared with small molecule activation to reveal the key problems in the cracking of NBPs. Finally, the challenges and potential directions are discussed to improve the overall efficiency in the photocatalytic cracking of NBPs. [ABSTRACT FROM AUTHOR]

Expanding the diversity of multi‐macrocyclic nanocarbons, particularly those with all‐benzene scaffolds, represents intriguing yet challenging synthetic tasks. Complementary to the existing synthetic approaches, here we report an efficient and modular post‐functionalization strategy that employs iridium‐catalyzed C−H borylation of the highly strained meta‐cycloparaphenylenes (mCPPs) and an mCPP‐derived catenane. Based on the functionalized macrocyclic synthons, a number of novel all‐benzene topological structures including linear and cyclic chains, polycatenane, and pretzelane have been successfully prepared and characterized, thereby showcasing the synthetic utility and potential of the post‐functionalization strategy. [ABSTRACT FROM AUTHOR]

Sb2S3 has been extensively used as light absorber for photoelectrochemical cell. However, its p‐type nature may result in the formation of Schottky junction with substrates, thus hindering the collection of photogenerated holes. Herein, an ultrathin CuxS layer is successfully engineered as the bottom junction for Sb2S3 for the first time. Capitalizing on its impressive electrical properties and superior optical properties, the CuxS layer exhibits a high work function of 4.90 eV, which causes the upward band bending of p‐type Sb2S3, forming a hole‐transparent structure with ohmic contact. The transparency of the ultrathin CuxS layer enables back‐illumination of the Sb2S3/CuxS platform, facilitating the integration of intricate catalyst layers for photoelectrochemical transformation. When modified with Pt nanoparticles, the photocurrent density reaches −5.38 mA cm−2 at 0 V vs. RHE, marking a fourfold increase compared to the photocathode without CuxS layer. When introducing a molecular hybrid TC‐CoPc@carbon black, a remarkable average photocurrent density of −0.44 mA cm−2 at the overpotential of 0 V is obtained for CO2 reduction reaction, while the photocurrent density is less than −0.03 mA cm−2 without CuxS. [ABSTRACT FROM AUTHOR]

Near infrared (NIR) emitter with circularly polarized phosphorescence (CPP), known as NIR CPP, has emerged as a key part in the research of cutting‐edge luminescent materials. However, it remains a challenge to obtain nanoclusters with NIR CPP activity. Here, we propose an asymmetric transformation approach to efficiently synthesize two pairs of chiral silver nanoclusters (R/S‐Ag29 and R/S‐Ag16) using an achiral Ag10 nanocluster as starting material in the presence of different concentration chiral inducer (R/S)‐1,1′‐binaphthyl‐2,2′‐diyl hydrogenphosphate (R/S‐BNP). R/S‐Ag29, formed in the low‐concentration R/S‐BNP, exhibits a unique kernel‐shell structure consisting of a distorted Ag13 icosahedron and an integrated cage‐like organometallic shell with a C3 symmetry, and possesses a superatomic 6‐electron configuration (1S2|1P4). By contrast, R/S‐Ag16, formed in the high‐concentration R/S‐BNP, features a sandwich‐like pentagram with AgI‐pure kernel. Profiting from the hierarchically chiral structures and superatomic kernel‐dominated phosphorescence, R/S‐Ag29 exhibits infrequent CPP activity in the second near‐infrared (975 nm) region, being the first instance of NIR‐II CPP observed among CPL‐active metal nanoclusters. This study presents a new approach to reduce the difficulty of de novo synthesis for chiral silver nanomaterials, and facilitates the design of CPP‐active superatomic nanoclusters in NIR region. [ABSTRACT FROM AUTHOR]

Herein, two atomically precise silver nanoclusters, Ag54 and Ag33, directed by inner anion templates (CrO42− and/or Cl−), are initially isolated as a mixed phase from identical reactants across a wide temperature range (20–80 °C). Interestingly, fine‐tuning the reaction temperature can realize pure phase synthesis of the two nanoclusters; that is, a metastable Ag54 is kinetically formed at a low temperature (20 °C), whereas such a system is steered towards a thermodynamically stable Ag33 at a relatively high temperature (80 °C). Electrospray ionization mass spectrometry illustrates that the stability of Ag33 is superior to that of Ag54, which is further supported by density functional theory calculations. Importantly, the difference in structural stability can influence the pathway of 1,4‐bis(pyrid‐4‐yl)benzene induced transformation reaction starting from Ag54 and Ag33. The former undergoes a dramatic breakage‐reorganization process to form an Ag31 dimer (Ag31), while the same product can be also achieved from the latter following a noninvasive ligand exchange process. Both the Ag54 and Ag33 have the potential for further remote laser ignition applications. This work not only demonstrates how temperature controls the isolation of a specific phase, but also sheds light on the structural transformation pathway of nanoclusters with different stability. [ABSTRACT FROM AUTHOR]