Iodine-mediated ring enlargement of the fullerene mixed peroxide C60(O)3(OAc)(OOtBu)3 affords iodine-containing open-cage fullerene C60(O)4(OAc)(I)(OOtBu)2 with a 15-membered orifice. Further modifications under acidic or basic conditions give derivatives with expanded or reshaped orifices. The iodo substituent remains intact under various conditions including reduction and oxidation. Single-crystal X-ray structures of key derivatives confirmed the cage architectures. Water encapsulation was observed in one derivative. These transformations demonstrate the unique reactivity of fullerene peroxides and provide a route to functionalized open-cage fullerenes as potential molecular containers.

In this study, we synthesized the first CAN (cancrinite)-typed zeolite-like oxonitridosilicates, Ln5Ca9O2(SiNO3)[Si12N24] (Ln = La and Ce). The crystal structure of La5Ca9O2(SiNO3)[Si12N24] was determined through single-crystal X-ray diffraction (SCXRD) data and neutron powder diffraction (NPD) data refinement. The compound crystallizes in hexagonal space group P63mc (No. 186) with a = 12.9875(2) Å, c = 5.2072(1) Å, and Z = 1. The anionic framework of La5Ca9O2(SiNO3)[Si12N24] is entirely constructed from [SiN4] tetrahedra, forming larger-sized composite building units, t-can and t-ato. The Ca2+ cations in the t-can cage contribute to balancing the charge difference originating from N3- substitution for O2- in La5Ca9O2(SiNO3)[Si12N24], which was revealed by the charge density difference calculation. The Ce3+-doped La5Ca9O2(SiNO3)[Si12N24] shows a broad-band orange-red emission peaking at λ = 630 nm under UV light excitation.

Corannulene (Cor) possesses an unique curved conjugated structure and remarkable photoelectric properties, yet its application is hindered by low triplet exciton utilization and unclear decay pathway regulation. This study proposes a strategy to regulate the spin-flipping process by precisely alignment of charge transfer (CT) state energy levels for enhancing triplet excitons harvesting in Cor. An electron donor-acceptor dye (Cor-PTZ) with phenothiazine (PTZ) donor and Cor acceptor is constructed. Cor-PTZ demonstrates thermally activated delayed fluorescence (TADF) emission with a small singlet-triplet energy gap, enabling fast spin-flipping for harvesting triplet excitons to support a maximum external quantum efficiency of 18.5% in OLEDs. Selective sulfur oxidation in Cor-PTZ yields Cor-PTZ-OX (X = 1, 2), which show elevated CT energy levels. This elevation suppresses reversed intersystem crossing, switching the dominant emission pathway from TADF to room-temperature phosphorescence (RTP). Nanosecond transient absorption spectroscopy and density functional theory calculation confirm that the low-lying triplet states are delocalized 3CT state in Cor-PTZ whereas the localized triplet state on Cor unit in Cor-PTZ-OX (X = 1, 2). This work reveals that the energy positioning of CT states dictates the spin-flipping, offering a general molecular design strategy for efficient triplet exciton utilization in curved polycyclic aromatic hydrocarbon systems.

Chloride recognition systems usually employ H-bonding with OH, NH, and CH groups and/or planar electron deficient pi-molecules. The present work reports the first open-cage fullerene derivative (Buckybowl) capable of encapsulating chloride anion selectively. Single crystal X-ray diffraction analysis and theoretical calculations reveal that the encapsulated chloride forms strong H-bonding with the hydroxyl group directly above the orifice, in addition to strong interactions with the electron deficient spherical pi-system. All other common anions including fluoride, iodide, and di-and polyatomic anions cannot enter the cavity of this open-cage fullerene derivative except for the bromide anion. Competitive encapsulation experiments with equimolar chloride and bromide mixtures demonstrate a remarkable 94:6 selectivity ratio in favor of chloride. Reversible hydration/dehydration of a carbonyl group along the rim of the 17-membered orifice serves as a chemical switch regulating transitions between open and closed states. The encapsulated chloride/bromide anion can be released upon dehydration to form the open state, followed by interaction with a silver cation. Alternatively, structural modification through 1,2-benzenediamine-mediated orifice expansion provides another pathway for halide release.

Electroreduction of CO2 or CO can produce renewable ethanol—a valuable industrial chemical. However, the limited energy and carbon efficiencies of reported systems present practical challenges. Here we introduce p-block elements into copper catalysts, enabling electrosynthesis of ethanol from CO for 200 h and delivering a full-cell energy efficiency of 22 Ethanol electrosynthesis from CO reduction is achieved using an oxygen-affinity-engineered copper alloy catalyst. Unlike conventional CO dimerization pathways, which yield diverse products, this catalyst selectively promotes the CO–CHx coupling route, enabling selective ethanol production.

In the paper, we report a highly robust and porous bimetallic Ti-MOF (designated Mg2Ti-ABTC) by utiliz- ing a trinuclear [Mg2TiO(COO)(6)] cluster and a tetradentate H4ABTC (3,3' ,5,5' - azobenzene tetracarboxylic acid) ligand. Mg2Ti-ABTC exhibited permanent porosity for N-2, CO2, CH4, C2H2, C2(2)H(4), and C2H6 gas adsorption. Further- more, Mg2Ti-ABTC exhibited outstanding photocatalytic activity in the oxidation of aromatic sulfides to the corre- sponding sulfoxides under ambient air conditions. Mechanism studies reveal that photoinduced holes (h(+)), the super- oxide radical ( O-2(-)), and singlet oxygen (O-1(2)) are pivotal species involved in the photocatalytic oxidation reaction. CCDC: 2442533, Mg2Ti-ABTC.

2,6-Diisopropylaniline reacts with an open-cage fullerene derivative with a 11-membered orifice and forms an open-cage derivative containing one imino group on the rim of the expanded orifice. Further treatment with Lewis acids leads to open-cage fullerenes with an 18-membered orifice. Instead of the direct addition process observed before for less bulky anilines, an electron transfer process takes place in the initial step in the present reaction with bulky 2,6-diisopropylaniline. As a result, the chemo-selectivity is completely different affording the mono imino open-cage derivative selectively.

The photocatalytic performance of metal-organic frameworks (MOFs) depends on the synergistic regulation of metal node, organic ligand, and topological structure, yet improving the recyclability and scalability of heterogeneous catalysts remains a significant challenge. Herein, we demonstrate that metal precursor selection critically controls both framework topology and catalytic activity in copper-based MOFs. Using a newly designed hexapyridyl triptycene ligand and deliberately varying copper salts (CuCN vs CuCl2), two topologically distinct MOFs, XJUM-1 and XJUM-2, with different pore size and photochemical properties were constructed. XJUM-2 exhibits a unique 6,4-connected 2-fold interpenetrated structure-unprecedented in cyanide-bridged systems-achieved through precise modulation of cyanide-bridge density. This structural control directly enhances charge separation, pore regularity, and catalytic performance. As a result, XJUM-2 delivers record-breaking activity for photocatalytic hydroboration of styrene (TOF = 86.4 h-1, the highest among Cu-MOFs), alongside exclusive anti-Markovnikov selectivity, broad substrate scope (40 examples), and robust recyclability (>92% yield over 5 cycles). Our work transcends conventional ligand/metal-node engineering, demonstrating that metal precursor choice is a critical, previously overlooked handle for programming MOF topology and reactivity in organic transformations.

One amino group of o-phenylenediamine undergoes nucleophilic addition to the carbonyl moiety of an open-cage fullerene containing a 9-membered ring orifice. Subsequent intramolecular cyclization under mild conditions generated a novel open-cage fullerene derivative featuring an enlarged 12-membered orifice. The unreacted amino group in this o-phenylenediamine adduct could be selectively oxidized to form a nitroso group, which was subsequently reduced back to an amino group using hydrochloric acid. This reduction process simultaneously induced dichlorination on the adjacent aromatic ring.

The regulation of luminescent properties is crucial for the development of multi-resonant thermally activated delayed fluorescence (MR-TADF) materials, which are widely used in organic light-emitting diodes (OLEDs). Herein, the rigid N^O and B^O units were incorporated into the multi-resonant B^N^O skeleton (PBN) with strong electron-donating ability, respectively, affording the compounds PBNNO and PBNBO. Theoretical calculations demonstrated that the emission properties of these MR-TADF materials were tuned by utilizing weak long-range charge transfer (CT) properties, which is mainly due to the stronger electron donating properties of PBN unit than N^O and B^O units. Experimental data prove that the weak long-range CT properties led to a red shift of the emission peak from 494 nm (PBN), 512 nm (PBNNO) to 524 nm (PBNBO), but their narrow full width at half-maximum (FWHM) is almost unchanged (35-38nm). This work offers valuable insights into the intricate relationship between long-range CT properties and photoluminescence behaviors in MR-TADF materials.

Taking advantage of the well-defined geometry of metal centers and highly directional metal-ligand coordination bonds, metal-organic frameworks (MOFs) have emerged as promising candidates for nonlinear optical (NLO) materials. In this work, taking a photoresponsive carboxylate triphenylamine derivative as an organic ligand, a bismuth-based MOF, Bi-NBC, NBC = 4',4‴,4‴″-nitrilotris(([1,1'-biphenyl]-4-carboxylic acid)) is obtained. Structure determination reveals that it is a potential NLO material derived from its noncentrosymmetric structure, which is finally confirmed by its rarely strong second harmonic generation (SHG) effect. Theoretical calculations reveal that the potential difference around Bi atoms is large; therefore, it leads to a strong local built-in electric field, which greatly facilitates the charge separation and transfer and finally improves the photocatalytic performance. Our results provide a reference for the exploration of MOFs with NLO properties.

Correction for 'A robust and porous titanium metal-organic framework for gas adsorption, CO2 capture and conversion' by Xuze Pan, et al., Dalton Trans., 2023, 52, 3896-3906, https://doi.org/10.1039/D2DT03158B.

The optical bandgaps of 2D halide perovskites (HPs) generally decrease with increasing inorganic layer thickness because of the diminishing quantum confinement (QC) effect. Here, we report a reverse bandgap trend in a class of Ge-based HPs, achieved through a judicious selection of organic cations, which exhibits an enhanced stereochemical lone pair expression (LPE) on the Ge2+ cation with increasing inorganic layer thickness. We find the enhanced LPE arises from cooperative interlayer compression and intralayer expansion on the inorganic lattice induced by a small spacer cation and a large cage A-cation, respectively. Experimental and theoretical studies show that such enhanced LPE can shift up the bandgap, which is significant enough to offset the QC effect, leading to the bandgap anomaly with tuning dimensionality. Our results reveal a previously underexplored avenue to tune the optical and electronic properties of 2D HPs by rationally controlling the LPE through interlayer and intralayer engineering.

The chemical reactivity of a 10-membered diketo open-cage fullerene C60(O)2(OOtBu)4 was investigated in an effort to reveal the unique reaction pattern of fullerene derivatives. Selective cleavage of peroxo O-O bonds was observed under thermolysis in the presence of iodine to form epoxy groups around the orifice. Opening of the epoxy groups leads to vicinal diol moiety, oxidation of which resulted in a new 10-membered keto-lactone open-cage fullerene derivative. Single crystal X-ray diffraction analysis showed that the size of the rectangular orifice is around 2.96x4.66 & Aring;.

A robust and porous Ti-MOF (LCU-505) has been synthesized based on a tetranuclear [Ti2Tb2] cluster. LCU-505 demonstrates an n-type semiconductor behavior and good photocatalytic activity in the degradation of organic dyes.

Correction for 'A robust and porous titanium metal-organic framework for gas adsorption, CO2 capture and conversion' by Xuze Pan, et al., Dalton Trans., 2023, 52, 3896-3906, https://doi.org/10.1039/D2DT03158B.

We report here a new type of metal fluoride cluster that can be stabilized inside fullerene via in situ fluorine encapsulation followed by exohedral trifluoromethylation, giving rise to rare-earth metal fluoride clusterfullerenes (FCFs) M2F@C-80(CF3) (M = Gd and Y). The molecular structure of Gd2F@C-80(CF3) was unambiguously determined by single-crystal X-ray analysis to show a mu(2)-fluoride-bridged Gd-F-Gd cluster with short Gd-F bonds of 2.132(7) and 2.179(7) & Aring;. The F-19 NMR spectrum of the diamagnetic Y2F@C-80(CF3) confirms the existence of the endohedral F atom, which exhibits a triplet with a large F-19-Y-89 coupling constant of 74 Hz and a high temperature sensitivity of the F-19 chemical shift of 0.057 ppm/K. Theoretical studies reveal the ionic Y-F bonding nature arising from the highest electronegativity of the F element and an electronic configuration of [Y2F](5+)@[C-80](5-) with an open-shell carbon cage, which thus necessitates the stabilization of FCFs by exohedral trifluoromethylation.

Benzylamine selectively adds to one of the two carbonyl groups on the 9-membered orifice to form an N , O -aminal moiety. Subsequent oxidation and hydrogen atom transfer lead to a decarboxylation process and formation of a nor [59]fullerene derivative.

A family of microporous titanium-containing metal-organic frameworks (denoted as M2Ti-CPCDC, M = Mn, Co, Ni) has been synthesized by using a bimetallic [M2Ti(mu(3)-O)(COO)(6)] cluster and a tritopic carbazole-based organic ligand H3CPCDC. M2Ti-CPCDC are stable and display permanent porosity for N-2 and CO2 uptake, ranking among the most porous titanium-based metal-organic frameworks. M2Ti-CPCDC crystals exhibit n-type semiconductor behavior. Further catalytic studies demonstrate that all M2Ti-CPCDC materials are applicable for triggering photo-oxidative reactions of amines in air. More specifically, amines with electron-donating groups afford the aldehydes as the main products, while amines bearing electron-withdrawing groups give rise to imines as the main product. Among them, Mn2Ti-CPCDC exhibit the best photocatalytic activity, with conversion of benzylamine up to 99% and selectivity of 99%. Mn2Ti-CPCDC could be recycled in at least three runs while retaining crystallinity and catalytic activity. The reaction mechanism indicates that photoinduced hole (h(+)), superoxide radical anion (O-2(-)), and singlet oxygen (O-1(2)) are the main active species involved in the photo-oxidation process.