Hiromitsu Uehara

Molecular decoding using luminescence from an entangled porous framework

Chemosensors detect a single target molecule from among several molecules, but cannot differentiate targets from one another. In this study, we report a molecular decoding strategy in which a single host domain accommodates a class of molecules and distinguishes between them with a corresponding readout. We synthesized the decoding host by embedding naphthalenediimide into the scaffold of an entangled porous framework that exhibited structural dynamics due to the dislocation of two chemically non-interconnected frameworks. An intense turn-on emission was observed on incorporation of a class of aromatic compounds, and the resulting luminescent colour was dependent on the chemical substituent of the aromatic guest. This unprecedented chemoresponsive, multicolour luminescence originates from an enhanced naphthalenediimide–aromatic guest interaction because of the induced-fit structural transformation of the entangled framework. We demonstrate that the cooperative structural transition in mesoscopic crystal domains results in a nonlinear sensor response to the guest concentration. Distinguishing closely related molecules using chemosensor materials is a continuing challenge. Here, an entangled porous coordination polymer is developed, which confines volatile organic compounds, and allows photoluminescence-based distinction of structurally similar aromatic molecules.

Morphology Design of Porous Coordination Polymer Crystals by Coordination Modulation

The design of crystal morphology, or exposed crystal facets, has enabled the development (e.g., catalytic activities, material attributes, and oriented film formation) of porous coordination polymers (PCPs) without changing material compositions. However, because crystal growth mechanisms are not fully understood, control of crystal morphology still remains challenging. Herein, we report the morphology design of [Cu(3)(btc)(2)](n) (btc = benzene-1,3,5-tricarboxylate) by the coordination modulation method (modulator = n-dodecanoic acid or lauric acid). A morphological transition (octahedron-cuboctahedron-cube) in the [Cu(3)(btc)(2)](n) crystal was observed with an increase in concentration of the modulator. By suitably defining a coarse-grained standard unit of [Cu(3)(btc)(2)](n) as its cuboctahedron main pore and determining its attachment energy on crystal surfaces, Monte Carlo coarse-grain modeling revealed the population and orientation of carboxylates and elucidated an important role of the modulator in determining the <100>- and <111>-growth throughout the crystal growth process. This comprehension, in fact, successfully led to designed crystal morphologies with oriented growth on bare substrates. Because selective crystal orientations on the bare substrates were governed by crystal morphology, this contribution also casts a new light on the unexplored issue of the significance of morphology design of PCPs.

Shape-Memory Nanopores Induced in Coordination Frameworks by Crystal Downsizing

Size Affects Shape Porous molecular framework materials can adopt a different phase when guest molecules absorb and uniformly distort the framework. Usually the framework returns to its original shape when the guests desorb. Sakata et al. (p. 193) noted that because surface stress drives this process, it might be avoided in smaller crystals. Indeed, a flexible porous coordination polymer, [Cu2(dicarboxylate)2(amine)]n, could retain the structure induced by guest molecules such as methanol if crystallites were made sufficiently small (submicrometer scale) and did so to a greater degree as the crystallite dimensions decreased. A porous material retains its framework shape after guest molecules desorb if its crystallites are sufficiently small. Flexible porous coordination polymers change their structure in response to molecular incorporation but recover their original configuration after the guest has been removed. We demonstrated that the crystal downsizing of twofold interpenetrated frameworks of [Cu2(dicarboxylate)2(amine)]n regulates the structural flexibility and induces a shape-memory effect in the coordination frameworks. In addition to the two structures that contribute to the sorption process (that is, a nonporous closed phase and a guest-included open phase), we isolated an unusual, metastable open dried phase when downsizing the crystals to the mesoscale, and the closed phase was recovered by thermal treatment. Crystal downsizing suppressed the structural mobility and stabilized the open dried phase. The successful isolation of two interconvertible empty phases, the closed phase and the open dried phase, provided switchable sorption properties with or without gate-opening behavior.

Sequential Functionalization of Porous Coordination Polymer Crystals

Crystal extractor: heterostructured porous coordination polymer crystals fabricated using epitaxial growth have two contradictory porous functions, namely size selectivity and high storage. The crystals not only extract linear petroleum molecules from a mixture with its branched isomer, even at very low concentrations of linear isomer (1 wt %), but also shows improved accumulation of the molecules in its pores.

Porous coordination polymer hybrid device with quartz oscillator: effect of crystal size on sorption kinetics.

A new strategy to synthesize monodispersed porous coordination polymer (PCP) nanocrystals at room temperature was developed and utilized for the formation of PCP thin films on gold substrates with fine control over the crystal sizes using the coordination modulation method. Hybridization of these PCP thin films with an environment-controlled quartz crystal microbalance system allowed determining the adsorption properties for organic vapors (methanol and hexane). In the case of high sensitivity (at the low-concentration dosing of analytes), the sensor response depended on the crystal size but not on the type of analyte. In contrast, at the high-concentration dosing, a clear dependence of the sorption kinetics on the analyte was observed due to significant sorbate-sorbate interaction.

Impact of crystal orientation on the adsorption kinetics of a porous coordination polymer–quartz crystal microbalance hybrid sensor

The hybridization of porous coordination polymers (PCPs) with electronic devices is a powerful strategy for developing systems that are suitable for advanced applications, such as chemical sensing. The quartz crystal microbalance (QCM) technique is one that allows minute mass changes to be resolved with a high temporal resolution, and the growth of PCP crystals that provide selective adsorption properties on a QCM substrate can facilitate the rapid detection of certain molecules from a gas or vapour mixture. Herein, we demonstrate the immobilization of the flexible PCP Zn(NO2-ip)(bpy) (Zn-CID-5; NO2-ip2− = 5-nitroisophthalate, bpy = 4,4′-bipyridine) on QCM substrates and investigate the adsorptive properties of the fabricated systems. Notably, the crystal orientation could be controlled by the anchoring of chemical functionalities on the substrate surface, or by the addition of coordination modulators (e.g. 4-phenylpyridine) at the time of growth of the PCP crystals on the substrates. Here, the crystal orientation plays a significant role in determining the detection kinetics of organic vapours (e.g. methanol), and the [010]-oriented case which displays the fastest adsorption kinetics among the samples tested is studied under mixed component (methanol–hexane) conditions to demonstrate its response profile. In all, the results demonstrate the potential utility of PCP/QCM hybrid systems in sensor applications, and also serve to highlight the importance of optimizing the physical orientation of crystal growth in such systems to maximize the overall performance of the system.

Trapping of a Spatial Transient State During the Framework Transformation of a Porous Coordination Polymer

Structural transformability accompanied by molecular accommodation is a distinguished feature of porous coordination polymers (PCPs) among porous materials. Conventional X-ray crystallography allows for the determination of each structural phase emerged during transformation. However, the propagation mechanism of transformation through an entire crystal still remains in question. Here we elucidate the structural nature of the spatial transient state, in which two different but correlated framework structures, an original phase and a deformed phase, simultaneously exist in one crystal. The deformed phase is distinctively generated only at the crystal surface region by introducing large guest molecules, while the remaining part of crystal containing small molecules maintains the original phase. By means of grazing incidence diffraction techniques we determine that the framework is sheared with sharing one edge of the original primitive cubic structure, leading to the formation of crystal domains with four mirror image relationships.

Dynamics of Photoelectrons and Structural Changes of Tungsten Trioxide Observed by Femtosecond Transient XAFS

The dynamics of the local electronic and geometric structures of WO3 following photoexcitation were studied by femtosecond time-resolved X-ray absorption fine structure (XAFS) spectroscopy using an X-ray free electron laser (XFEL). We found that the electronic state was the first to change followed by the local structure, which was affected within 200 ps of photoexcitation.

Deprotonation of a dinuclear copper complex of 3,5-diamino-1,2,4-triazole for high oxygen reduction activity

A dinuclear copper(II) complex of 3,5-diamino-1,2,4-triazole is one of the highly active copper-based catalysts for the oxygen reduction reaction (ORR) in basic solutions. Our in situ X-ray absorption near edge structure measurements revealed that deprotonation of the triazole ligand might cause coordination geometrical changes, resulting in the enhancement of the ORR activity.

Preparation and structure of a single Au atom on the TiO2(110) surface: control of the Au–metal oxide surface interaction

Three-dimensional Au structures on bare and organic-compound-modified TiO2(110) surfaces were interrogated by Au L3-edge polarization dependent total reflection fluorescence X-ray absorption fine structure (PTRF-XAFS) spectroscopy. On the bare TiO2(110) surface, icosahedral Au55 nanoclusters were the main product found. When the surfaces were modified with ortho or meso mercaptobenzoic acid (o-MBA or m-MBA), Au was atomically dispersed. Sulfur atoms in the o- and m- MBA formed strong covalent bonds with Au to produce stable Au-MBA (o- and m- forms) surface complexes. On the other hand, only oxygen atoms on the surface did not make a strong enough interaction to stabilize the Au species. We discuss how the Au species formed on the modified TiO2(110) surface and the possibility to control the Au structure by the surface modification method.