Design of the gas-diffusion process in a porous material is challenging because a contracted pore aperture is a prerequisite, whereas the channel traffic of guest molecules is regulated by the flexible and dynamic motions of nanochannels. Here, we present the rational design of a diffusion-regulatory system in a porous coordination polymer (PCP) in which flip-flop molecular motions within the framework structure provide kinetic gate functions that enable efficient gas separation and storage. The PCP shows substantial temperature-responsive adsorption in which the adsorbate molecules are differentiated by each gate-admission temperature, facilitating kinetics-based gas separations of oxygen/argon and ethylene/ethane with high selectivities of ~350 and ~75, respectively. Additionally, we demonstrate the long-lasting physical encapsulation of ethylene at ambient conditions, owing to strongly impeded diffusion in distinctive nanochannels.

Two-dimensional polymeric nanosheets have recently gained much attention, particularly top-down nanosheets such as graphene and metal chalcogenides originating from bulk-layered mother materials. Although molecule-based bottom-up nanosheets manufactured directly from molecular components can exhibit greater structural diversity than top-down nanosheets, the bottom-up nanosheets reported thus far lack useful functionalities. Here we show the design and synthesis of a bottom-up nanosheet featuring a photoactive bis(dipyrrinato)zinc(II) complex motif. A liquid/liquid interfacial synthesis between a three-way dipyrrin ligand and zinc(II) ions results in a multi-layer nanosheet, whereas an air/liquid interfacial reaction produces a single-layer or few-layer nanosheet with domain sizes of >10 μm on one side. The bis(dipyrrinato)zinc(II) metal complex nanosheet is easy to deposit on various substrates using the Langmuir–Schäfer process. The nanosheet deposited on a transparent SnO2 electrode functions as a photoanode in a photoelectric conversion system, and is thus the first photofunctional bottom-up nanosheet.

Herein, we report that a new flexible coordination network, NiL (L=4-(4-pyridyl)-biphenyl-4-carboxylic acid), with diamondoid topology switches between non-porous (closed) and several porous (open) phases at specific CO and CH pressures. These phases are manifested by multi-step low-pressure isotherms for CO or a single-step high-pressure isotherm for CH . The potential methane working capacity of NiL approaches that of compressed natural gas but at much lower pressures. The guest-induced phase transitions of NiL were studied by single-crystal XRD, in situ variable pressure powder XRD, synchrotron powder XRD, pressure-gradient differential scanning calorimetry (P-DSC), and molecular modeling. The detailed structural information provides insight into the extreme flexibility of NiL . Specifically, the extended linker ligand, L, undergoes ligand contortion and interactions between interpenetrated networks or sorbate-sorbent interactions enable the observed switching.

Let your light shine: The first example of a heteroleptic bis(dipyrrinato)zinc(II) complex, 7a, was synthesized from two types of dipyrrins prepared by a new deboration protocol for BODIPYs. Complex 7a showed a higher fluorescence quantum yield (0.76 in toluene) than the corresponding homoleptic complexes 5a and 6. The superiority of 7a as a luminophore was more prominent in more polar CH2Cl2 (see picture).

Dipyrrins serve as monovalent bidentate ligand molecules that coordinate to various cations. Their BF 2 complexes, 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene and its derivatives (BODIPYs), exhibit excellent photostability, strong light absorption, and high fluorescence quantum yield, thereby encouraging their application in various fields, e.g., as biological and biomedical fluorescent markers. Dipyrrin may also accept a wide variety of metal ions spontaneously. However, dipyrrin metal complexes have been disregarded from materials science research. This review article summarizes recent progress in bis(dipyrrinato)metal(II) and tris(dipyrrinato)metal(III) complexes from the viewpoint of materials chemistry. Section 2 describes a series of efforts aimed to realize intense luminescence superior to or comparable with that of BODIPYs. The spontaneous coordination of these complexes enables them to construct self-assembled nanoarchitectures, such as supramolecules and coordination polymers that form one-dimensional nanowires, two-dimensional nanosheets, and metal-organic frameworks. Section 3 describes such alluring molecular superstructures. Section 4 discusses potential applications based on these nanoarchitectures, such as thermoelectric and photoelectric conversion. aimed to realize intense luminescence superior to or comparable with that of BODIPYs. Section 3 discusses the selfassembly of bis and tris(dipyrrinato)metal complexes, which results in the formation of alluring nanoarchitectures, such as supramolecules and coordination polymers giving rise to onedimensional nanowires, two-dimensional nanosheets, and metal-organic frameworks (MOFs) and porous coordination polymers (PCPs). Section 4 describes potential applications based on these nanoarchitectures. Pursuit of bright luminescenceA plain BODIPY shows intense absorption and bright fluorescence at approximately 500 nm, which are derived from the 1 π-π * transition of the dipyrrinato ligand. 5-16 The absorption and fluorescence may be redshifted upon the introduction of substituents on the dipyrrinato ligand, covering the region 500-900 nm. BODIPYs are good fluorophores even in polar solvents such as water. In sharp contrast, dipyrrin metal complexes have long been believed to be non-luminescent or weakly luminescent. This drawback seriously reduces the value of dipyrrinato-metal complexes in applications in which they serve, for example, as photosensitizers. In this section, the authors concentrate on efforts to improve the luminescent ability of bis and tris(bisdipyrrinato)metal complexes. For comprehensive knowledge on the whole types of luminescent dipyrrinato-metal complexes (i.e. mono(dipyrrinato)metal complexes with ancillary ligands other than dipyrrins), please see a comprehensive review article contributed by Baudron. 2

The prevalence of the condensed phase, interpenetration, and fragility of mesoporous coordination polymers (meso-PCPs) featuring dense open metal sites (OMSs) place strict limitations on their preparation, as revealed by experimental and theoretical reticular chemistry investigations. Herein, we propose a rational design of stabilized high-porosity meso-PCPs, employing a low-symmetry ligand in combination with the shortest linker, formic acid. The resulting dimeric clusters (PCP-31 and PCP-32) exhibit high surface areas, ultrahigh porosities, and high OMS densities (3.76 and 3.29 mmol g, respectively), enabling highly selective and effective separation of CH from CH/CO mixtures at 298 K, as verified by binding energy (BE) and electrostatic potentials (ESP) calculations.

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We analyzed stable carbon and nitrogen isotope ratios in a sample of human and nonhuman mammal bones excavated from the Yoshigo and Inariyama shell mounds of the Late-Final Jomon periods in Aichi Prefecture, Japan, with a view to determining individual dietary differences. To investigate possible reasons for the dietary variations identified, we related isotope ratios to sex and tooth ablation patterns. At both sites, large intra-site variations in δ 13 C and δ 15 N values were found, compared with other Jomon populations previously studied, suggesting higher than usual levels of dietary variability, and at both sites there was a positive correlation between δ 13 C and δ 15 N values. The diet of the Jomon people at both these sites had two main protein sources: marine (marine finfish and shellfish) and terrestrial (C 3 plants and terrestrial mammals) protein. The intra-site variability is probably explained by consumption of these resources in different proportions. Analysis of the Yoshigo shell mound data indicated that sex is one of the factors determining dietary difference. It was also found that individual differences in diet in Yoshigo males are greater than in females. This pattern was repeated in the Inariyama shell mound data. Dietary differences were found to be related to ritual tooth ablation characteristics, particularly in males. At Inariyama, type 4I ritual tooth ablation was associated with comparatively greater dependency on terrestrial resources, while type 2C tooth ablation was associated with greater dependency on marine resources. This may indicate that type 4I males engaged predominantly in hunting, and type 2C males in fishing, as a means of food acquisition. These results are possibly the earliest evidence of occupational differentiation in the Jomon people.