Self-Assembly of Cluster-Mediated 3D Catenanes with Size-Specific Recognition Behavior.

Although interlocked three-dimensional molecules display unique properties associated with their spatial structures, their synthesis and study of their host-guest properties remain challenging. We report the formation of a novel [2]catenane, [Et4N]@[(Tp*WS3Cu3Cl)2(cis-bpype)3]2(OTf)5 ([Et4N][1](OTf)5), by self-assembly of the cluster node [Tp*WS3Cu3Cl]+ and the organic linker (Z)-1,2-diphenyl-1,2-bis(4-(pyridin-4-yl)phenyl)ethene (cis-bpype). Single-crystal X-ray and NMR analyses established that [1]4+ is formed by the interpenetration of two cluster-organic cages. Unique cation-in-cation host-guest complexes were observed with this catenane. The crystalline, empty catenane was formed by taking advantage of the electrostatic repulsion-induced weak binding of the host. Encapsulation experiments also reveal that the empty catenane can adaptively encapsulate cations such as [Et4N]+ and [Pr4N]+ in the cross cavity but is unable to encapsulate [Bu4N]+ and [Me4N]+, although the size of the latter is compatible with that of the cavity. Theoretical calculations and volume analysis allow to unravel the ingenious role of catenane structures and the interplay between electrostatic repulsion and attractive noncovalent interactions for size-specific recognition behavior in host-guest systems involving species with similar electric charges.

Visible Light and Microwave-Mediated Rapid Trapping and Release of Singlet Oxygen Using a Coordination Polymer.

Due to its high reactivity and oxidative strength, singlet oxygen (1 O2 ) is used in a variety of fields including organic synthesis, biomedicine, photodynamic therapy and materials science. Despite its importance, the controlled trapping and release of 1 O2 is extremely challenging. Herein, we describe a one-dimensional coordination polymer, CP1, which upon irradiation with visible light, transforms 3 O2 (triplet oxygen) to 1 O2 . CP1 consists of CdII centers bridged by 9,10-bis((E)-2-(pyridin-4-yl)vinyl)anthracene ligands which undergo a [4+2] cycloaddition reaction with 1 O2 , resulting in the generation of CP1-1 O2 . Using microwave irradiation, CP1-1 O2 displays efficient release of 1 O2 , over a period of 30 s. In addition, CP1 exhibits enhanced fluorescence and has an oxygen detection limit of 97.4 ppm. Theoretical calculations reveal that the fluorescence behaviour is dominated by unique through-space conjugation. In addition to describing a highly efficient approach for the trapping and controlled release of 1 O2 , using coordination polymers, this work also provides encouragement for the development of efficient fluorescent oxygen sensors.

Exploitation of a Half-Conjugate Polydentate Salamo-Salen Hybrid Ligand and Its Two Phenoxide-Bridged Heterohexanuclear 3d-s Double-Helical Cluster Complexes.

A half-conjugate polydentate Salamo-Salen hybrid ligand, H5L, containing two unique N2O2 pockets was first designed so that these metal ions in the complexes appear in different coordination modes. Two heterohexanuclear 3d-s double-helical cluster complexes, [Zn4Ca2L2(µ1-OAc)2(EtOH)2]·2EtOH (1; EtOH = ethanol) and [Zn4Sr2L2(µ2-OAc)2(MeOH)2]·2CH2Cl2 (2; MeOH = methanol), are reported that are formed through the reaction of H5L with zinc(II) and calcium(II) acetate or strontium(II) acetate, respectively. IR spectral analysis of the two complexes showed the existence of monodentate- and bidentate-coordinated acetate ions. The fluorescence properties of the ligand and its two heterohexanuclear complexes were explored in MeOH and water solutions, separately. In addition, theoretical calculations (density functional theory, interaction region indicator, and bond order) were performed to further understand the formation of a single-molecular double helix and the electron distribution characteristics of the two complexes.

In situ observation of a stepwise [2 + 2] photocycloaddition process using fluorescence spectroscopy.

Using highly sensitive and selective in situ techniques to investigate the dynamics of intermediates formation is key to better understand reaction mechanisms. However, investigating the early stages of solid-state reactions/transformations is still challenging. Here we introduce in situ fluorescence spectroscopy to observe the evolution of intermediates during a two-step [2 + 2] photocycloaddition process in a coordination polymer platform. The structural changes and kinetics of each step under ultraviolet light irradiation versus time are accompanied by the gradual increase-decrease of intensity and blue-shift of the fluorescence spectra from the crystals. Monitoring the fluorescence behavior using a laser scanning confocal microscope can directly visualize the inhomogeneity of the photocycloaddition reaction in a single crystal. Theoretical calculations allow us to rationalize the fluorescence behavior of these compounds. We provide a convenient strategy for visualizing the solid-state photocycloaddition dynamics using fluorescence spectroscopy and open an avenue for kinetic studies of a variety of fast reactions.

A novel bifunctional-group salamo-like multi-purpose dye probe based on ESIPT and RAHB effect: Distinction of cyanide and hydrazine through optical signal differential protocol.

A novel bifunctional-group multi-purpose dye probe p-TNS has been designed and synthesized. The probe p-TNS has unique excited-state intramolecular proton transfer (ESIPT) and resonance-assisted hydrogen bonding (RAHB) coupled system, was confirmed to detect cyanide and hydrazine by blocking the ESIPT effect. Cyanide can change the fluorescence of the solution from bright green to orange-red (116 nm Stokes shift), while hydrazine causes the bright green fluorescence to be quenched. The recognition mechanism of the probe p-TNS to CN- and N2H4 was proposed reasonably through spectral characterizations and theoretical calculations. Combined with theoretical calculations, it was speculated that the solvent dependence may be caused by the ICT effect in the molecule. The probe p-TNS could be prepared into test strips for the detection of cyanide and hydrazine. In addition, the probe molecule can also be used to detect trace amounts of cyanide in agricultural products, and respond to gaseous hydrazine by direct contact, indicating that the probe p-TNS has good practical application prospects. Therefore, this molecular framework provides a new way of thinking about detecting multiple target substances.