Article-Journal

May 18, 2020

Abstract Organic and molecule-based magnets are not easily attainable, as introduction of stable paramagnetic centers to pure organic systems is particularly challenging. Crystalline covalent organic frameworks (COFs) with high designability and chemical diversity constitute ideal platforms to access intriguing magnetic phenomena of organic materials. In this work, we proposed a general approach to attain unpaired electron spin and metal-free magnetism in narrow-band COFs by chemical doping. By using density functional theory calculations, we found that dopants with energy-matched frontier orbitals to COFs not only inject charges but also further localize them through orbital hybridization and the formation of a supramolecular charge-transfer complex. The localized electronic states ensure that stable paramagnetic centers can be introduced to nonmagnetic COFs. On the basis of these discoveries, we designed two new COFs with narrow valence bands, which show prospective magnetism after doping with iodine. Further, we unraveled the magnetic anisotropy in two-dimensional COFs and demonstrated that both spin-conduction and magnetic interactions can be effectively modulated by manipulating the building blocks of COFs. Our work highlights a practical route to attain magnetism in COFs and other organic materials, which show great potential for applications in organic spintronic devices.

May 18, 2020

Abstract The precise control of the molecular position and orientation of its nanoscale assembly on atomic crystals is pivotal for fabricating hybrid organic/inorganic van der Waals heterostructures with targeted functionalities. Recently, we observed the assembly of oleamide into nanoribbons, orienting exclusively along a crystallographic direction on a variety of atomic crystals. Motivated by this observation, we designed a series of long-chain alkanes, alkenes, and their derivatives with −OH, −COOH, and −CONH2 terminal groups to unveil how chemical units regulate the orientation of suparamolecular assembly by density functional theory calculations. We found that the cis-C═C bond can increase the rigidity of long alkyl chains, tailoring angles and van der Waals interactions between them, while the −CONH2 group facilitates intermolecular hydrogen bonds. Either of these two moieties is required for the oriented assembly on both hexagonal and orthorhombic atomic lattices. We predicted that nanoribbons formed by long-chain cis-alkene and derivatives orient along the zigzag direction on graphene and 32° deflected from the armchair direction on black phosphorene, which were supported by the experiment. The fundamental understandings toward the chemical group regulated intermolecular interactions, and their interplay in the oriented supramolecular assembly is expected to substantially expedite the design and controlled synthesis of organic/inorganic van der Waals heterostructures using the bottom-up method.

Nov 27, 2019

Abstract The assembly of atomically precise clusters into superstructures has tremendous potential in structural tunability and applications. Here, we report a series of single-cluster nanowires, single-cluster nanorings, and three-dimensional superstructure assemblies built by POM clusters. By stepwise tuning of interactions at molecular levels, the configurations can be varied from single-cluster nanowires to nanorings. A series of single-cluster nanostructures in different configurations can be achieved with up to 15 kinds of POM clusters. The single-cluster nanowires and three-dimensional superstructures perform enhanced activity in the catalytic and electrochemical sensing fields, illustrating the universal functionality of single-cluster assemblies.

Jul 26, 2019

Abstract Two-dimensional (2D) transition metal dichalcogenides (TMDCs) with layered structures provide a unique platform for exploring the effect of number of layers on their fundamental properties. However, the thickness scaling effect on the chemical properties of these materials remains unexplored. Here, we explored the chemically induced phase transition of 2D molybdenum disulfide (MoS2) from both experimental and theoretical aspects and observed that the critical electron injection concentration and the duration required for the phase transition of 2D MoS2 increased with decreasing number of layers. We further revealed that the observed dependence originated from the layer-dependent density of states of 2H-MoS2, which results in decreasing phase stability for 2H-MoS2 with increasing number of layers upon electron doping. Also, the much larger energy barrier for the phase transition of monolayer MoS2 induces the longer reaction time required for monolayer MoS2 as compared to multilayer MoS2. The layer-dependent phase transition of 2D MoS2 allows for the chemical construction of semiconducting-metallic heterophase junctions and, subsequently, the fabrications of rectifying diodes and all 2D field effect transistors and thus opens a new avenue for building ultrathin electronic devices. In addition, these new findings elucidate how electronic structures affect the chemical properties of 2D TMDCs and, therefore, shed new light on the controllable chemical modulations of these emerging materials.

May 21, 2018

Abstract Supramolecular catalysis aims to modulate chemical reactions on both selectivity and rate by taking advantage of supramolecular chemistry. However, due to the effect of product inhibition, supramolecular catalysts are usually added in stoichiometric amounts. Herein, we report a supramolecular catalysis system in which 1% of the supramolecular catalyst, cucurbit[8]uril, is able to significantly accelerate the photodimerization of Brooker’s merocyanine. This catalytic process is realized in a cyclic manner because the photodimerized product can be spontaneously replaced by monomeric reactants via competitive host–guest complexation. Thus, a catalytic amount of cucurbit[8]uril is sufficient to accomplish photodimerization within 10 min. This line of research will enrich the field of supramolecular catalysis and allow the development of more efficient catalytic systems.

Oct 13, 2017

Abstract Probing the crystallographic orientation of two-dimensional (2D) materials is essential to understand and engineer their properties. However, the nondestructive identification of the lattice orientations of various 2D materials remains a challenge due to their very thin nature. Here, we identify the crystallographic structures of various 2D atomic crystals using molecules as probes by utilizing orientation-dependent molecule–substrate interactions. We discover that the periodic atomic packing of 2D materials guides oleamide molecules to assemble into quasi-one-dimensional nanoribbons with specific alignments which precisely indicate the lattice orientations of the underlying materials. Using oleamide molecules as probes, we successfully identify the crystallographic orientations of ~12 different 2D materials without degrading their intrinsic properties. Our findings allow for the nondestructive identification of the lattice structure of various 2D atomic crystals and shed light on the functionalization of these 2D materials with supramolecular assembly.

Aug 29, 2017

Abstract Solar cells based on organic inorganic hybrid metal halide perovskites have exhibited a rapid increase of power conversion efficiency (PCE). Perovskite solar cells involving mixed cations, especially recently reported Cs doping, have shown huge potential to improve PCE as well as device stability. However, when doping Cs into CH3NH3PbI3 (MAPbI3) and [HC(NH2)2]3PbI3 (FAPbI3), CsPbI3 could segregate from the perovskite phase, affecting the performance negatively. In addition, despite improved charge transfer was predicted for oriented film along <112>/<200> directions, the fabrication is still on the way and rarely reported. Herein, an ultra-smooth perovskite film oriented along <112>/<200> directions is created for the first time, with a homogeneous tetragonal phase of (MAPbI3)1−x(CsPbBr3)x. The preferentially precipitated heavily Cs-doped perovskite, and the lowered surface energy of (112) and (200) planes, verified by DFT calculations, are responsible for the orientation. The improved charge transfer and suppressed trap states in the oriented film substantially improved the performance. Upon an optimal doping ratio of 0.1, a PCE of 17.6% was achieved, together with remarkable improvements in stability under UV irradiance and in ambient atmosphere.

Jun 27, 2016

Abstract Herein, we have developed a one-pot method for the fabrication of one-dimensional core/shell microrods with tunable shell compositions by the introduction of additives. Crystalline dimethyl melamine hydrochloride was utilized as the core, while melamine derivatives with different functional groups, such as pyrene, thiophene and naphthalene diimide, served as additives to regulate the core morphology and were adsorbed as the shell. The length and width of these one-dimensional structures can be tuned by varying the molar ratio of core and shell molecules as well as their total concentration. Through X-ray diffraction, the detailed molecular arrangements within the core of the microrods were revealed, and the selective effect of additives on specific crystal faces was evaluated. It is anticipated that this work may provide a facile approach for the fabrication of one-dimensional functional materials.

Jun 3, 2015