Mechanical Bond Induced Enhancement and Purification of Pyrene Emission in the Solid State.

To address key concerns on solid-state pyrene-based luminescent materials, we propose a novel and efficient mechanical bond strategy. This strategy results in a transformation from ACQ to AIE effect and a remarkable enhancement of pyrene emission in the solid state. Moreover, an unusual purification of emission is also achieved. Through computational calculation and experimental characterisation, finally determined by X-ray diffraction analysis, we prove that the excellent emissions result from mechanical bond induced refinement of molecular arrangements, including reduced π-π stacking, well-ordered packing and enhanced structural stability. This work demonstrates the potential of mechanical bond in the field of organic luminescent molecules, providing a new avenue for developing high-performance organic luminescent materials.

CD-MOF-1 Growth on Polysaccharide Gels through Only C2-OH/C3-OH or C5-O/C6-OH Group Formed Four-Coordinated K+ Ions for Developing Porous Biogels.

The γ-cyclodextrin (γ-CD) metal-organic frameworks (CD-MOF-1) consist of γ-CD and potassium (K+) ions through coordinating an eight-coordinated K+ ion with two C5-linked oxygen and C6-linked hydroxyl (C5-O/C6-OH) groups in the primary faces of adjacent γ-CD units and two C2- and C3-linked hydroxyl (C2-OH/C3-OH) groups in the secondary faces. Herein, we found polysaccharide gels with only C2-OH/C3-OH or C5-O/C6-OH groups in pyranoid rings can form four-coordinated K+ ions and then coordinate γ-CD in a KOH solution for CD-MOF-1 growth. Exposure of C2-OH/C3-OH or C5-O/C6-OH groups in polysaccharide gels is important to form active four-coordinated K+ ions. Mechanism supporting this work is that four-coordinated K+ ion sites are first formed after coordinating C2-OH/C3-OH groups in pectin and then coordinating C5-O/C6-OH groups in the primary faces of γ-CD units. Alternatively, four-coordinated K+ ions with C5-O/C6-OH groups in chitosan can coordinate the C2-OH/C3-OH groups in the secondary faces of γ-CD units. Mechanism of CD-MOF-1 growing on pectin and chitosan gels through the proposed four-coordinated K+ ions is also universally applicable to other polysaccharide gels with similar C2-OH/C3-OH or C5-O/C6-OH groups such as alginate gel. Based on this mechanism, we developed pectin and chitosan gel-based CD-MOF-1 composites and exemplified applications of them in antibacterial and organic dye removal. To help future research and applications of this mechanism, we share our theoretical assumption for further investigations that any matrices with an ortho-hydroxyl carbon chain or ortho-hydroxyl ether structures may form four-coordinated K+ ions for CD-MOF-1 growth. The proposed mechanism will broaden the development of novel CD-MOF-1 composites in various fields.

A Carbazole-1,8-Disulfonamide-Derived Cryptand Receptor for Anion Recognition.

A novel cryptand-like anion receptor 1 was synthesized in reasonable yield by a one-step condensation reaction. The UV-vis spectroscopic titrations indicated that cryptand 1 bound AcO- in preference to other monovalent anions (including its competing F- and H2PO4-) in CH3CN, generating a 1:1 binding complex with Ka = 51,000 M-1. Moreover, the crystal structures revealed that the acetate ion was encapsulated inside the cryptand's cavity in a 1:1 manner, through multiple N-H···O hydrogen bonds (although having two different crystal forms).

Unveiling the Unique Roles of Metal Coordination and Modulator in the Polymorphism Control of Metal-Organic Frameworks.

Polymorphism control of metal-organic frameworks is highly desired for elucidating structure-property relationships, but remains an empirical process and is usually done in a trial-and-error approach. We adopted the rarely used actinide cation Th4+ and a ditopic linker to construct a series of thorium-organic frameworks (TOFs) with a range of polymorphs. The extraordinary coordination versatility of Th4+ cations and clusters, coupled with synthetic modulation, gives five distinct phases, wherein the highest degree of interpenetration (threefold) and porosity (75.9 %) of TOFs have been achieved. Notably, the O atom on the capping site of the nine-coordinated Th4+ cation can function as a bridging unit to interconnect neighboring secondary building units (SBUs), affording topologies that are undocumented for other tetravalent-metal-containing MOFs. Furthermore, for the first time HCOOH has been demonstrated as a bridging unit of SBUs to further induce structural complexity. The resulting TOFs exhibit considerably different adsorption behaviors toward organic dyes, thus suggesting that TOFs represent an exceptional and promising platform for structure-property relationship study.

A quantum crystallographic approach to short hydrogen bonds.

In this work we use high-resolution synchrotron X-ray diffraction for electron density mapping, in conjunction with ab initio modelling, to study short O-H⋯O and O+-H⋯O- hydrogen bonds whose behaviour is known to be tuneable by temperature. The short hydrogen bonds have donor-acceptor distances in the region of 2.45 Šand are formed in substituted urea and organic acid molecular complexes of N,N'-dimethylurea oxalic acid 2 : 1 (1), N,N-dimethylurea 2,4-dinitrobenzoate 1 : 1 (2) and N,N-dimethylurea 3,5-dinitrobenzoic acid 2 : 2 (3). From the combined analyses, these complexes are found to fall within the salt-cocrystal continuum and exhibit short hydrogen bonds that can be characterised as both strong and electrostatic (1, 3) or very strong with a significant covalent contribution (2). An additional charge assisted component is found to be important in distinguishing the relatively uncommon O-H⋯O pseudo-covalent interaction from a typical strong hydrogen bond. The electron density is found to be sensitive to the extent of static proton transfer, presenting it as a useful parameter in the study of the salt-cocrystal continuum. From complementary calculated hydrogen atom potentials, we attribute changes in proton position to the molecular environment. Calculated potentials also show zero barrier to proton migration, forming an 'energy slide' between the donor and acceptor atoms. The better fundamental understanding of the short hydrogen bond in the 'zone of fluctuation' presented in a salt-cocrystal continuum, enabled by studies like this, provide greater insight into their related properties and can have implications in the regulation of pharmaceutical materials.

Divergent Synthesis of Double Heterohelicenes as Strong Chiral Double Hydrogen-Bonding Donors.

We developed a very efficient and expandable divergent approach initiated by a direct electrophilic borylation at phenyl rings to synthesize a series of double heterohelicenes. Their π-extended structures with pristine zigzag nitrogen (N)-boron (B)-nitrogen (N) edges offer them substantial physical properties and strong double hydrogen-bond donating capability. The isolated (P,P) and (M,M) enantiomers exhibit circularly polarized luminescence in response to hydrogen-bonding interactions.

Supramolecular Proton Conductors Self-Assembled by Organic Cages.

Proton conduction is vital for living systems to execute various physiological activities. The understanding of its mechanism is also essential for the development of state-of-the-art applications, including fuel-cell technology. We herein present a bottom-up strategy, that is, the self-assembly of Cage-1 and -2 with an identical chemical composition but distinct structural features to provide two different supramolecular conductors that are ideal for the mechanistic study. Cage-1 with a larger cavity size and more H-bonding anchors self-assembled into a crystalline phase with more proton hopping pathways formed by H-bonding networks, where the proton conduction proceeded via the Grotthuss mechanism. Small cavity-sized Cage-2 with less H-bonding anchors formed the crystalline phase with loose channels filled with discrete H-bonding clusters, therefore allowing for the translational diffusion of protons, that is, vehicle mechanism. As a result, the former exhibited a proton conductivity of 1.59 × 10-4 S/cm at 303 K under a relative humidity of 48%, approximately 200-fold higher compared to that of the latter. Ab initio molecular dynamics simulations revealed distinct H-bonding dynamics in Cage-1 and -2, which provided further insights into potential proton diffusion mechanisms. This work therefore provides valuable guidelines for the rational design and search of novel proton-conducting materials.