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Abstract When aiming at the direct use of CO2 for the preparation of advanced/value-added materials, the synthesis of CO2/olefin copolymers is very appealing but challenging. The δ-lactone 3-ethylidene-6-vinyltetrahydro-2H-pyran-2-one (EVP), synthesized by telomerization of CO2 with 1,3-butadiene, is a promising monomer. However, its chemoselective ring-opening polymerization (ROP) is hampered by unfavorable thermodynamics and the competitive polymerization of highly reactive C=C double bonds under usual conditions. Herein, we report the chemoselective ROP of EVP using a phosphazene/urea binary catalyst, affording exclusively a linear unsaturated polyester poly(EVP)ROP, with a molar mass (M n) up to 16.1 kg·mol−1 and a narrow distribution (Ð

Abstract Creating specific noble metal/metal‐organic framework (MOF) heterojunction nanostructures represents an effective strategy to promote water electrolysis but remains rather challenging. Herein, a heterojunction electrocatalyst is developed by growing Ir nanoparticles on ultrathin NiFe‐MOF nanosheets supported by nickel foam (NF) via a readily accessible solvothermal approach and subsequent redox strategy. Because of the electronic interactions between Ir nanoparticles and NiFe‐MOF nanosheets, the optimized Ir@NiFe‐MOF/NF catalyst exhibits exceptional bifunctional performance for the hydrogen evolution reaction (HER) (η10 = 15 mV, η denotes the overpotential) and oxygen evolution reaction (OER) (η10 = 213 mV) in 1.0 m KOH solution, superior to commercial and recently reported electrocatalysts. Density functional theory calculations are used to further investigate the electronic interactions between Ir nanoparticles and NiFe‐MOF nanosheets, shedding light on the mechanisms behind the enhanced HER and OER performance. This work details a promising approach for the design and development of efficient electrocatalysts for overall water splitting.

Abstract Using highly sensitive and selective in situ techniques to investigate the dynamics of intermediates formation is key to better understand reaction mechanisms. However, investigating the early stages of solid-state reactions/transformations is still challenging. Here we introduce in situ fluorescence spectroscopy to observe the evolution of intermediates during a two-step [2 + 2] photocycloaddition process in a coordination polymer platform. The structural changes and kinetics of each step under ultraviolet light irradiation versus time are accompanied by the gradual increase-decrease of intensity and blue-shift of the fluorescence spectra from the crystals. Monitoring the fluorescence behavior using a laser scanning confocal microscope can directly visualize the inhomogeneity of the photocycloaddition reaction in a single crystal. Theoretical calculations allow us to rationalize the fluorescence behavior of these compounds. We provide a convenient strategy for visualizing the solid-state photocycloaddition dynamics using fluorescence spectroscopy and open an avenue for kinetic studies of a variety of fast reactions.

Solid-state photochemical reactions of olefinic compounds provide access to organic cyclic molecules with specific configurations but the precise control of the stereochemistry in these reactions remains challenging. Here, the authors demonstrate control of the regiospecific configurations of C=C groups and the intermediates by varying temperatures in multi-step thermal and photoinduced ring opening and closing reactions using a single-crystal coordination polymer platform.

Designing and building unique cage assemblies attract increasing interest from supramolecular chemists but remain synthetically challenging. Herein, we propose the use of a flexible vertex with adjustable angles to selectively form highly distorted tetrahedral and octahedral cages, for the first time, in which the flexible vertex forms from the synergistic effect of coordination and covalent interactions. The inherent interligand angle of the vertex can be modulated by guest anions present, which allows for the fine-tuning of different cage geometries. Furthermore, the reversible structural transformation between tetrahedral and octahedral cages was achieved by anion exchange monitored by mass spectrometric technique, the smaller anions favoring tetrahedral cages, while the larger anions supporting octahedral cages. Additionally, the KBr-based cage thin films exhibited prominent enhancement of their third-order NLO responses in two or three orders of magnitude compared to those obtained for their corresponding solutions. This work not only provides a new methodology to build irregular polyhedral structures in a controlled and tunable way but also provides access to new kinds of promising functional optical materials.

Summary: Many methods exist for the synthesis of covalent organic frameworks (COFs), but precise morphology control allowing the tailoring of core-shell and yolk-shell nanostructures has been elusive, mainly due to poor control of the reaction-diffusion processes. Herein, we propose the precise regulation of the COF generation and decomposition rates and their relationship with the diffusion rate of COF species during the synthesis, which enables a successful preparation of core-shell, yolk-shell, hollow-spherical, and multiple yolk-shell COF structures with tunable sizes ranging from 200 to 1,400 nm. Formed COF structures can serve as nanoreactors or nanocontainers, with the shell layer providing molecular-size selectivity determined by the nanopore size demonstrated here using Suzuki coupling reactions with phenylboronic acid, which produce a size-cutoff efficiency for halogenated aromatics approaching 100%. The precise morphology design and control of COF particles and hybrids may help enhance application efficiencies and provide access to new functionalities for COF materials.