Two cyclometalated Pt(ii) complexes showing reversible phosphorescence switching due to grinding-induced destruction and crystallization-induced formation of supramolecular dimer structure

Two Pt(ii) complexes 1 and 2 reveal similar supramolecular dimer structure, in which two [Pt(dfppy/ppy)(pbdtmi)]+ cations connect each other through the π⋯π stacking interaction. Thus these complexes show reversible phosphorescence switching by grinding and crystallization with toluene.

BN-Embedded Perylenes

Transition metal catalyzed coupling reaction strategy has been utilized in the synthesis of two novel BN-perylenes starting from halogenated BN-naphthalene derivatives. The molecular structures and packing modes of BN-perylenes were confirmed by NMR spectroscopy and X-ray single-crystal diffraction experiments. Their photophysical properties were further investigated using UV-vis and fluorescence spectroscopy and DFT calculations. Interestingly, the isosteric BN-insertion in perylene system resulted in stronger π-π stacking interaction both in solid and solution phases. The synthesized BN-perylenes are proved to be highly stable and thus provide a new valuable platform for novel organic materials applications which is otherwise inaccessible to date.

Revealing the chirality origin and homochirality crystallization of Ag14 nanocluster at the molecular level

Although chirality is an ever-present characteristic in biology and some artificial molecules, controlling the chirality and demystifying the chirality origin of complex assemblies remain challenging. Herein, we report two homochiral Ag14 nanoclusters with inherent chirality originated from identical rotation of six square faces on a Ag8 cube driven by intra-cluster π···π stacking interaction between pntp− (Hpntp = p-nitrothiophenol) ligands. The spontaneous resolution of the racemic (SD/rac-Ag14a) to homochiral nanoclusters (SD/L-Ag14 and SD/R-Ag14) can be realized by re-crystallizing SD/rac-Ag14a in acetonitrile, which promotes the homochiral crystallization in solid state by forming C–H···O/N hydrogen bonds with nitro oxygen atoms in pntp− or aromatic hydrogen atoms in dpph (dpph = 1,6-bis(diphenylphosphino)hexane) on Ag14 nanocluster. This work not only provides strategic guidance for the syntheses of chiral silver nanoclusters in an all-achiral environment, but also deciphers the origin of chirality at molecular level by identifying the special effects of intra- and inter-cluster supramolecular interactions.

Pyridinedicarboxylate-Tb(III) Complex-Based Luminescent Probes for ATP Monitoring

The pyridinedicarboxylate-Tb(III) complexes, TbPDC and Tb(PDC)3, as luminescent probes for ATP monitoring have been conveniently prepared and characterized by FT-IR, 1H-NMR, ESI-MS, UV-Vis, excitation, and emission spectroscopy. Interestingly, these two Tb(III) complexes were quenched by ATP by a similar mechanism via π-π stacking interaction between the chelating ligand and adenine moiety. The ability of luminescent probes applied for the determination of ATP in aqueous solution has been investigated. The dynamic ranges for the quantification of ATP are within 10−90 μM and 10−100 μM with detection limits of 7.62 and 11.20 μM for TbPDC and Tb(PDC)3, respectively. The results demonstrated that these luminescent probes would be a potential candidate assay for ATP monitoring in hygiene assessment.

The Face-to-Face σ-Hole···σ-Hole Stacking Interactions: Structures, Energies, and Nature

The existence of the π···π stacking interaction is well-known. Similarly, it is reasonable to assume the existence of the σ-hole···σ-hole stacking interaction. In this work, the structures, energies, and nature of the face-to-face σ-hole···σ-hole stacking interactions in the crystal structures have been investigated in detail by the quantum chemical calculations. The calculated results clearly show that the face-to-face σ-hole···σ-hole stacking interactions exist and have unique properties, although their strengths are not very significant. The energy component analysis reveals that, unlike many other dispersion-dominated noncovalent interactions in which the induction energies always play minor roles for their stabilities, for the face-to-face σ-hole···σ-hole stacking interaction the contribution of the induction energy to the total attractive energy is close to or even larger than that of the electrostatic energy. The structures, energies, and nature of the face-to-face σ-hole···σ-hole stacking interactions confined in small spaces have also been theoretically simulated. One of the important findings is that encapsulation of the complex bound by the face-to-face σ-hole···σ-hole stacking interaction can tune the electronic properties of the container.

catena-Poly[[bis(quinolin-8-amine-κ2 N,N′)cadmium(II)]-μ-cyanido-κ2 N:C-[dicyanidonickel(II)]-μ-cyanido-κ2 C:N]

In the title compound, [CdNi(C9H8N2)2(CN)4] n , the Cd and Ni atoms both lie on centres of inversion in space group P21/c. The Cd atom is coordinated by two bidentate quinolin-8-amine ligands and by the N atoms of two cyano ligands, while the square planar Ni atom is coordinated by the C atoms of four cyano ligands. These units form a one-dimensional coordination polymer containing an (–NC—Ni—CN—Cd–) n backbone, and the coordination polymer chains are linked into a three-dimensional array by a combination of N—H...N and C—H...N hydrogen bonds, augmented by a π–π stacking interaction.

Visible colorimetric dosimetry of UV and ionizing radiations by a dual-module photochromic nanocluster

Radiation dosimeters displaying conspicuous response of irradiance are highly desirable, owing to the growing demand of monitoring high-energy radiation and environmental exposure. Herein, we present a case of dosimetry based on a discrete nanocluster, [Th6(OH)4(O)4(H2O)6](TPC)8(HCOO)4∙4DMF∙H2O (Th-SINAP-100), by judiciously incorporating heavy Th6 polynuclear centers as radiation attenuator and organic linkers as photo-responsive sensor. Interestingly, dual-module photochromic transitions upon multiple external stimuli including UV, β-ray, and γ-ray are integrated into this single material. The striking color change, and more significantly, the visible color transition of luminescence in response to accumulating radiation dose allow an on-site quantitative platform for naked-eye detection of ionization radiations over a broad range (1–80 kGy). Single crystal X-ray diffraction and density functional theory calculations reveal that the dual-module photochromism can be attributed to the π(TPC) → π*(TPC) intermolecular charge transfer driven by enhanced π-π stacking interaction between the adjacent TPC moieties upon irradiation.

The crystal structures of three disordered 2-substituted benzimidazole esters

The crystal structures of three benzimidazole esters containing aryl or heterocyclic substituents at position 2 are reported, and all three exhibit disorder of molecular entities. In ethyl 1-methyl-2-[4-(prop-2-ynoxy)phenyl]-1H-benzimidazole-5-carboxylate, C20H18N2O3, (I), the prop-2-yn-1-oxyphenyl unit is disordered over two sets of atomic sites having effectively equal occupancies, 0.506 (5) and 0.494 (5). The propyl substituent in ethyl 1-propyl-2-(pyren-1-yl)-1H-benzimidazole-5-carboxylate, C29H24N2O2, (II), is disordered over two sets of atomic sites having occupancies 0.601 (8) and 0.399 (8), and the ester unit in ethyl 1-methyl-2-(5-chloro-3-methyl-1-phenyl-1H-pyrazol-4-yl)-1H-benzimidazole-5-carboxylate, C21H19ClN4O2 (III), is disordered over two sets of atomic sites having occupancies 0.645 (7) and 0.355 (7). In each of the C—H...π(arene) hydrogen bonds in (I), the donor and acceptor form parts of different disorder components, so that no continuous aggregation is possible. The molecules of (II) are linked by a single C—H...O hydrogen bond into C(10) chains, which are linked into sheets by a π–π stacking interaction, whereas those of (III) are just linked into C(13) chains, again by a single C—H...O hydrogen bond. Comparisons are made with the structures of some related compounds.

Enantioselective, Catalytic Multicomponent Synthesis of Homoallylic Amines Enabled by Hydrogen-Bonding and Dispersive Interactions

We report a one-step catalytic, enantioselective method for the preparation of homoallylic <i>N</i>-Boc amines directly from acetals. Reactive iminium ion intermediates are generated <i>in situ</i> through the combination of an acetal, a chiral thiourea catalyst, trialkylsilyl triflate, and <i>N</i>-Boc carbamate, and are subsequently trapped by a variety of allylsilane nucleophiles. No homoallylic ether byproducts are detected, consistent with allylation of the iminium intermediate being highly favored over allylation of the intermediate oxocarbenium ion. Acetals derived from aromatic aldehydes possessing a variety of functional groups and substitution patterns yield homoallylic amines with excellent levels of enantiomeric enrichment. Experimental and computational data are consistent with an anchoring hydrogen-bond interaction between the protoiminium ion and the amide of the catalyst in the enantiodetermining transition state, and with stereodifferentiation achieved through specific non-covalent interactions (NCIs) with the catalyst pyrenyl moiety. Evidence is provided that the key NCI in the major pathway is a π-stacking interaction, contrasting with the cation–π interactions invoked in previously studied reactions promoted by the same family of aryl-pyrrolidino-H-bond-donor catalysts.