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A porous metal–organic framework for imidazole-dependent anhydrous proton conduction and photocatalytic CO2 reduction.

(Br−)CH3-Pyridinium-MOF-1 integrated reactive Lewis acid sites and Br− nucleophilic anions and exhibited efficient catalytic activity for the cycloaddition of CO2 to epoxides.

An acylamide-functionalized metal–organic framework has been synthesized via a solvothermal reaction and its proton conductivity is increased by nearly two orders of magnitude after the removal of guest DMA molecules.

The nonlinear optical responses of carbon nanohoop derivatives increase significantly with the increasing number and the length of π-bridges.

A CO2 bridged photocatalytic interface between a nickel metal–organic framework and ruthenium pyridine for high-efficiency photoreduction of diluted CO2.

This review systematically summarizes the various structures of molybdenum clusters and their potential applications in different fields, including proton conductivity, organic catalysts, photoelectric reduction of CO2, nanomedicines and others.

To compare homoleptic [2]catenanes and single rings consisting of gold(i) thiolates, the geometric and electronic structures, absorption spectra, binding energy, interaction energy and composition of intramolecular forces were studied theoretically.

Nondoped organic light-emitting diodes (OLEDs) are of paramount importance for display and lighting applications owing to their advantages of facile fabrication and outstanding stability. However, nondoped OLEDs achieving extraordinary electroluminescence (EL) performance and low turn-on voltage (

Precise synthesis of polyoxometalates (POMs) is important for the fundamental understanding of the relationship between the structure and function of each building motif. However, it is a great challenge to realize the atomic-level tailoring of specific sites in POMs without altering the major framework. Herein, we report the first case of Ce-mediated molecular tailoring on the unprecedented gigantic {Mo132}, which has a closed structural motif involving a never seen {Mo110} decamer. Such capped wheel {Mo132} undergoes a rare quasi-isomerism with known {Mo132} ball displaying different optical behaviors. Experiencing an ‘Inner-On-Outer’ binding process with the substituent of {Mo2} reactive sites in {Mo132}, the site-specific Ce ions drive the dissociation of {Mo2*} clipping sites and finally give rise to a predictable half-closed product {Ce11Mo96}. By virtue of the tailor-made open cavity, the {Ce11Mo96} achieves high proton conduction, nearly two orders of magnitude than that of {Mo132}. This work offers a significant step toward the controllable assembly of POM clusters through a Ce-mediated molecular tailoring process for desirable properties.

Photoredox catalysis can be induced to activate organic substrates or to modulate the oxidation state of transition-metal catalysts via unique single-electron transfer processes, so as to achieve c...

Herein, a N-rich metal-organic framework (MOF) with four kinds of cages, Zn

Constructing high-quality white organic light-emitting diodes (WOLEDs) remains a big challenge because of high demands on the electroluminescence (EL) performance including high efficiency, excellent spectral stability, and low roll-off simultaneously. To achieve effective energy transfer and trap-assisted recombination in the emissive layer, herein, four Ir(III) phosphors, namely

DFT and TD-DFT calculations were performed to turn conventional non-TADF units into high-lying reverse intersystem crossing D–A–D-type TADF emitters.

The domain difference determines the effect degree of the ratio of the third component and the ratio can react in turn to regulate the internal charge transfer mode under a certain domain difference in ternary organic solar cells.

A MOF with strong deep blue light emission and high quantum efficiency has high selectivity and sensitivity for detecting 2,6-dichloro-4-nitroaniline.

The DHP derivative has more excellent NLO properties, while the CPD derivative possesses TADF properties, showing an interesting “seesaw” phenomenon.

Three new cucurbit[6]uril-based metal–organic rotaxane networks functionalized by a sulfonic group (–SO3H) have been designed and synthesized.

We develop the effective modification strategy based on molecular engineering of s-triazine and its derivatives to improve the photoelectric performance of all-inorganic perovskites (AIP) for the first time. The surface modification strategy with cyanuric acid successfully increases the PLQY of AIP from 40.55% to 88.15%, and significantly enhances the current of the AIP film under 3 V by almost 20-fold (from 4.44 mA to 81.20 mA). This work has proven the effectiveness of improving the photoelectric performances of AIP via s-triazine and its derivatives and also suggested the potential risks of reducing the photoelectric performance of AIP due to inappropriate substituents in conjugated organic ligands.

Two POMOFs, CUST-631 and CUST-632, were synthesized by a hydrothermal method and then were directly prepared as electrode materials to explore the electrocatalytic properties for reduction of BrO3− and NO2− ions and oxidation properties towards AA.

The room-temperature phosphorescence of 1,8-naphthalimide was activated by doping it into aromatic dicarboxylic acids. The doping system gives a bright yellow afterglow and 1,8-naphthalimide and isophthalic acid (0.02 mol% doping content) afford a phosphorescent lifetime of 403 ms and a quantum yield of 4.2%. Both energy transfer from the host to the guest and the formation of an intermolecular hydrogen-bonding network are responsible for the observed efficient and long-lived phosphorescence.

Heterogeneous zinc powder can not only transform into organic zinc reagents to promote the Ni(ii) transmetalation but also regulate the oxidation state from Ni(ii) to active Ni(i) accordingly for achieving the NiI–NiIII–NiI catalytic cycle.

The anionic framework In-MOF exchanged with NH4+ and Rubpy can serve as a potential proton conductor and photocatalyst for CO2 photoreduction.

A new Co-MOF with splendid stability can act as an excellent heterogeneous catalyst to activate peroxymonosulfate, exhibiting highly efficient organic dye degradation in aquatic environments.

The structure of the DHP–CPD core was modified chemically by different acceptor and donor groups, showing interesting NLO switch characteristics upon protonation.

Two new transition metal–organic frameworks (CUST-751 and CUST-752) have been designed and synthesized, which can be used as multiresponsive fluorescence sensors to detect Fe3+ and Cr2O72−. Moreover, CUST-751 also can detect TNP.

Molecular isomeric engineering is employed to construct efficient orange-red Ir(iii) complexes for WOLEDs and understand the intrinsic structure–property relationship.

Spin-unrestricted DFT and spin-unrestricted TDDFT calculations were performed to systematically investigate the correlation between the electron donating ability of donors and photophysical properties in D–A luminescent radicals.

An unprecedented fully reduced {MoV60} POM served as a cheap and robust molecular light-absorber model possessing wide light absorption and was applied to build a co-sensitized solar cell photoelectronic device.

A novel metal-anchored COF was synthesized and applied to photocatalytic conversion of CO2 and H2O into widely adjustable syngas. The reaction intermediates, electron transfer pathway and syngas generation mechanism were discussed in depth.

This highlight focuses on the strategies to improve the photocatalytic reduction of low-concentration CO2 by MOF materials, including the modification of MOF skeletons and the preparation of MOF composites or MOF derivatives. It will provide insights into the rational design of heterogeneous catalysts to achieve efficient reduction of low-concentration CO2.

The anhydrous proton conductivity of Im@IEF-11 resulting from the integration of imidazole and porous IEF-11 has been investigated, and the highest proton conductive value can reach up to 7.64 × 10

With the increasing global energy demand and environmental problems, the photoreduction of CO2 into valuable chemical materials is considered to be an ideal way to recycle carbon resources. Naturally, the...

A POMOF with [W10O32]4− and mononuclear cobalt clusters as connecting nodes, which can be used as a photocatalyst to reduce low concentrations of CO2 in flue gas to generate syngas.

This work reveals the structural characteristics to realize the positive correlation between JSC and VOC, and further proposes the energy differences as descriptors to predict the positive correlation for the promotion of PCE.

The conductive polymer PANI was coated on the surface of POM-based electrodes by the method of electrodeposition for improving the capacitive performance, and the corresponding solid-state SCs exhibited excellent capacitive performance.

Polyoxometalates (POMs) have a broad array of applied platforms with well-characterized catalysis including photocatalysis to achieve aliphatic C(sp3)-H bond functionalization. However, the reaction mechanism of POMs in organic transformation remains unknown due to the complexity of POM structures. Here, a challenging [W10O32]4-/Ni metallaphotoredox-catalyzed C(sp3)-H arylation of alkane has been investigated by density functional theory (DFT) calculations. The calculation revealed that the superficial active center located in bridged oxygen of *[W10O32]4- is responsible for the abstraction of a foreign hydrogen atom and the activation of a C(sp3)-H bond. Furthermore, we discussed this activated process using the direct activation model of the C(sp3)-H σ-bond to deepen our mechanistic understanding of POM mediated C-H bond activation via the hydrogen atom transfer (HAT) pathway. Specifically, comparing three common mechanisms for nickel catalysis inducing by Ni0, NiI, and NiII to construct a C-C bond, the nickel catalytic cycle induced by the NiI active catalyst is profitable in kinetics and thermodynamics. Finally, a radical mechanism merging the ([W10O32]4--*[W10O32]4--[HW10O32]4--[W10O32]4-) decatungstate reductive quenching cycle, ([HW10O32]4--[H2W10O32]4--[HW10O32]4-) electron relay, and (NiI-NiII-NiI-NiIII-NiI) nickel catalytic cycle is proposed to be favorable. We hope that this work would provide a better understanding of the unique catalytic activity of decatungstate anions for the direct functionalization of the C(sp3)-H bond.

Building metal-organic frameworks (MOFs) covalently modified by onium halides is a promising approach to develop efficient MOF-based heterogeneous catalysts for the cycloaddition of CO

Pd-catalyzed borylation of fluorobenzene was theoretically studied. DFT calculations revealed that the reaction occurs through an unprecedented 3 + 6-membered ring transition state, in which one LiHMDS (HMDS = hexamethyldisilazane) acts as a ligand and another LiHMDS is essential to provide Li···N and Li···F interactions, overcoming the large destabilization of the strong phenyl-F bond distortion. The characteristic feature of LiHMDS was elucidated by comparing it with HMDS and NaHMDS analogues.

Chirality is a fundamental feature of a structure, and chiral systems have been widely applied in many fields. This work mainly paid attention to effects of chiral interaction on molecular nonlinear optical (NLO) response. To this aim, D- or L-type alanine (Ala) with right or left handness respectively were added into chiral single-wall carbon nanotube (CNT) in this work. As a result by theoretical calculation, homo-chiral complex, namely, right-handed CNT with (D)-type Ala (or left-handed CNT with (L)-type Ala) would bring little stronger Ala-CNT interaction and larger first-order static hyperpolarizability βtot. In addition, βtot difference arising from charge transfer transition could be tuned by changing length and (or) chirality of CNT. These consequences were meaningful for further exploration of controlling molecular NLO properties by chirality.

Direct conversion of diluted CO