Two Ag(I)-Containing Supramolecular Coordination Polymers Constructed from the Multidentate N-donor Ligand 1-((1H-1,2,4-triazol-1-yl)methyl)-3,5-bis(3-pyridyl)-1,2,4-triazole Based on Hydrogen-Bonding and π–π Interactions: Syntheses,Crystal Structures,Optical Band Gaps and Luminescent Properties

Two Ag(I)-based coordination polymers, namely [Ag₂(3,3′-tmbpt)(o-Hbdc)₂]·H₂O (1) and [Ag₈(3,3′-tmbpt)₄(1,2,4-Hbtc)₄(H₂O)] (2) (3,3′-tmbpt?=?1-((1H-1,2,4-triazol-1-yl)methyl)-3,5-bis(3-pyridyl)-1,2,4-triazole, o-H₂bdc?=?1,2-benzenedicarboxylic acid and 1,2,4-H₃btc?=?1,2,4-benzenetricarboxylic acid), have been synthesized. Single-crystal X-ray diffraction analyses, elemental analyses, infrared spectra, powder X-ray diffraction analyses and thermogravimetric analyses have been carried out to characterize the structures of 1 and 2. Compound 1 shows a (3,4)-connected 2D layered structure with a Schläfli symbol of (4²·6)(4²·6³·8). The intermolecular O–H···O hydrogen-bonding interactions extend the 2D layer into a 3D supramolecular architecture. Compound 2 exhibits a (3,3)-connected double-layered structure with a Schläfli symbol of (4·8·10)₂(8²·10)₂. The intermolecular C–H···O hydrogen-bonding interactions link the double-layers to form a 3D supramolecular architecture. Moreover, there are intramolecular and intermolecular π–π interactions in 1 and 2, which stabilize the whole 3D supramolecular architectures. The band gaps of 1 and 2 are 3.19 and 3.09 eV, respectively, indicating the potential of 1 and 2 as semiconductive materials with wide band gaps. Moreover, 1 and 2 emit intense blue-green light, which may be potential photoactive materials.

Graphic Abstract

Two Ag(I)-based 3D supramolecular coordination polymers constructed from a multidentate N-donor ligand and two aromatic polycarboxylate anions via hydrogen-bonding and π–π interactions have been synthesized and characterized. The band gaps and photoluminescent properties of the compounds have been studied.

     

On the Extreme Oxidation States of Iridium

It has recently been suggested that the oxidation states of Ir run from the putative ?III in the synthesized solid Na₃[Ir(CO)₃] to the well‐documented +IX in the species IrO₄⁺. Furthermore, [Ir(CO)₃]^3? was identified as an 18‐electron species. A closer DFT study now finds support for this picture: The orbitals spanned by the 6s,6p,5d orbitals of the iridium are all occupied. Although some have considerable ligand character, the deviations from 18 e leave the orbital symmetries unchanged. The isoelectronic systems from Os^?IV to Au^?I behave similarly, suggesting further possible species. To paraphrase Richard P. Feynmann “there is plenty of room at the bottom”.     

Facile synthesis of 1-naphthols through a copper-catalyzed arylation of methyl ketones with o-bromoacetophenones

The coupling reactions of simple methyl ketones with o-bromoacetophenones and subsquential cyclization reactions were realized to produce a range of 1-naphthols. These cascade reactions were initiated by a rare Cu-catalyzed arylation reaction of methyl ketones with aromatic bromides.     

Synthesis of polybutadienes with controllable microstructure by a novel binary Nd(3-NBSO3)3/alkylaluminum catalyst system

The polymerization of 1,3-butadiene was examined by using a novel halogen-free neodymium m-nitrobenzenesulfonate(Nd(3-NBSO3)3·donors)/alkylaluminum binary catalyst system. The catalyst showed fairly high activity and controllable selectivity. The microstructure of the resultant polymer was adjustable by variation of electron donor and/or the alkylaluminum. 13C-NMR and thermal analysis demonstrate that the produced polybutadienes have stereo-block chain structures of cis-1,4 and trans-1,4 segments with adjustable Tm and Tc. The neodymium sulfonate-based catalyst is believed to be significant in regulating the chain structure of polydienes and in exploring 1,3-diene polymerization mechanism.     

Relative Stability of Multiple Bonds between Germanium and Stibium. A Theoretical Study

Substituent effects on the potential energy surface of XGeSb (X=H, Li, Na, BeH, MgH, BH₂, AlH₂, CH₃, SiH₃, NH₂, PH₂, OH, SH, F, and Cl) were investigated by using B3LYP/Def2‐TZVP, B3PW91/Def2‐ TZVPP CCSD (T)//B3LYP/Def2‐TZVP methods. The isomers include structures with formal double (Ge=SbX) and triple (Xge=Sb) bonds to germanium‐stibium, so a direct comparison of these types of species is possible. Our model calculations indicate that electropositively substituted Ge=SbX species are thermodynamically and kinetically more stable than their isomeric Xge=Sb molecules. Moreover, the theoretical findings suggest that only the organic substitutions (such as CH₃) can make triply bonded Xge=Sb molecule more stable than the doubly bonded Ge=SbX species.     

Two New Triterpene Saponins from the Seed Residue of Hippophae rhamnoides L.

Two new triterpene saponins, named hippophosides E and F ( 1 and 2 , resp.), together with two known compounds, were isolated from the seed residue of Hippophae rhamnoides L. Their structures were elucidated on the basis of chemical and spectral analysis, including 1D‐ and 2D‐NMR and HR‐MS experiments, and by comparison with literature data.     

Aggregation-induced dual-color luminogen with enhanced chiroptical property

Science China Chemistry -     

Dyeing behavior and mechanism of Crocein Orange G on carboxymethyl cotton fabric

Cellulose - Traditional cotton fiber dyeing requires an abundance of salt, which leads to environmental pollution. Consequently, decreasing or eliminating the use of salt has become the primary...