Discrete Rectangles,Prisms, and Heterometallic Cages from a Conjugated Cp*Rh‐Based Building Block

By carefully selecting an existing synthetic strategy and suitable coordination subunits, constructing desired coordination geometries is no longer that difficult to accomplish. Herein, a new strategy to construct a series of unprecedented structures by using conjugated Cp*Rh‐based complex BN‐OTf (Cp*=η⁵‐C₅Me₅) as the building block is proposed. DFT calculations revealed extensive delocalized π bonds in the subunit. With BN‐OTf , rectangular macrocycles TN‐bpy and TN‐bpe were controllably synthesized. Single‐crystal XRD studies confirmed one‐dimensional stacking channels for the tetranuclear structure. Notably, the starting ligand imidazole‐4,5‐dicarboxylate was found to act not only as a tetradentate but also as a hexadentate ligand that can coordinate to further metal ions. Subsequently, [4 Rh+1 M] heterometallic complexes HMZ (M=Cu and Zn) were accessed by chelating borderline hard/soft Lewis acids. With TN‐Linker or HMZ , two routes resulted in the [8 Rh+2 M] heterometallic cages HMC (M=Cu and Zn) with excellent crystallinity and stability. Surprisingly, when BN‐OTf bonded to rhodium itself, triangular prisms TP‐Linker were obtained with high solubility after being linked by bipyridine linkers. Both the X‐ray structure and ¹H NMR spectrum confirmed the novel isomerization of the triangular structures. All of the compounds were obtained in high yields and were fully characterized by ¹H NMR spectroscopy, elemental analysis, IR spectroscopy, and in most cases single‐crystal X‐ray structure determination.     

Intramolecular Aminoboration of Unfunctionalized Olefins

A direct and catalyst‐free method for the intramolecular aminoboration of unfunctionalized olefins is reported. In the presence of BCl₃ (1 equiv) as the sole boron source, intramolecular aminoboration of sulfonamide derivatives of 4‐penten‐1‐amines, 5‐hexen‐1‐amines, and 2‐allylanilines proceeded readily without the use of any catalyst. The boronic acids obtained after hydrolysis could be converted into the corresponding pinacol borates in a straightforward manner by treatment with pinacol under anhydrous conditions.     

Crystalline Hetero‐Stereocomplexed Polycarbonates Produced from Amorphous Opposite Enantiomers Having Different Chemical Structures

Stereocomplexation is the stereoselective interaction between two opposite enantiomeric polymers through an interlocked orderly assembly. Most studies focus on the stereocomplex formation from the crystalline opposite enantiomers having the identical structure; nevertheless, rare examples were reported regarding the crystalline stereocomplexes from enantiomeric polymers having different chemical structures. Herein we show a strategy for polymer orderly assembly through the formation of crystalline hetero‐stereocomplexed polymeric materials by the cocrystallization of amorphous isotactic polycarbonates with different chemical structures and opposite configurations. The behaviors in the crystalline state are significantly different from that of the component enantiomeric polymers or their homo‐stereocomplexes. This study is expected to open up a new way to prepare various semicrystalline materials having a wide variety of physical properties and degradability.     

Palladium‐Catalyzed Asymmetric Reductive Heck Reaction of Aryl Halides

Asymmetric reductive Heck reaction of aryl halides is realized in high stereoselectivity. Hydrogen‐bond donors, trialkylammonium salts in a glycol solvent, were used to promote halide dissociation from neutral arylpalladium complexes to access cationic, stereoselective pathways.     

Rhodium‐Catalyzed Enantioselective Intramolecular CH Silylation for the Syntheses of Planar‐Chiral Metallocene Siloles

Reported herein is the rhodium‐catalyzed enantioselective C? H bond silylation of the cyclopentadiene rings in Fe and Ru metallocenes. Thus, in the presence of (S)‐TMS‐Segphos, the reactions took place under very mild conditions to afford metallocene‐fused siloles in good to excellent yields and with ee values of up to 97 %. During this study it was observed that the steric hindrance of chiral ligands had a profound influence on the reactivity and enantioselectivity of the reaction, and might hold the key to accomplishing conventionally challenging asymmetric C? H silylations.     

Organic Crystals with Near‐Infrared Amplified Spontaneous Emissions Based on 2′‐Hydroxychalcone Derivatives: Subtle Structure Modification but Great Property Change

A series of highly efficient deep red to near‐infrared (NIR) emissive organic crystals 1 – 3 based on the structurally simple 2′‐hydroxychalcone derivatives were synthesized through a simple one‐step condensation reaction. Crystal 1 displays the highest quantum yield (Φ_f) of 0.32 among the reported organic single crystals with an emission maximum (λ_em) over 710 nm. Comparison between the bright emissive crystals 1 – 3 and the nearly nonluminous compounds 4 – 7 clearly gives evidence that a subtle structure modification can arouse great property changes, which is instructive in designing new high‐efficiency organic luminescent materials. Notably, crystals 1 – 3 exhibit amplified spontaneous emissions (ASE) with extremely low thresholds. Thus, organic deep red to NIR emissive crystals with very high Φ_f have been obtained and are found to display the first example of NIR fluorescent crystal ASE.     

Directed meta‐Selective Bromination of Arenes with Ruthenium Catalysts

A Ru‐catalyzed direct C? H activation/meta‐bromination of arenes bearing pyridyl, pyrimidyl, and pyrazolyl directing groups has been developed. A series of bromo aryl pyridines and pyrimidines have been synthesized, and further coupling reactions have also been demonstrated for a number of representative functionalized arenes. Preliminary mechanistic studies have revealed that this reaction may proceed through radical‐mediated bromination when NBS is utilized as the bromine source. This type of transformation has opened up a new direction for the radical non‐ipso functionalization of metal with regard to future C? H activation development that would allow the remote functionalization of aromatic systems.     

Syntheses,Structures, and Luminescent Properties of d10 Coordination Polymers with 2‐(4‐Carboxyphenyl)‐imidazo[4, 5‐f]‐1, 10‐phenanthroline and 1, 3‐Benzenedicarboxylate Derivatives

Four Zn^II/Cd^II coordination polymers (CPs) based on 2‐(4‐carboxy‐phenyl)imidazo[4, 5‐f]‐1, 10‐phenanthroline (HNCP) and different derivatives of 5‐R‐1, 3‐benzenedicarboxylate (5‐R‐1, 3‐BDC) (R = NO₂, H, OH), [Zn(HNCP)(5‐NO₂‐1, 3‐BDC)]_n ( 1 ), [Cd(HNCP)(5‐NO₂‐1, 3‐BDC)]_n ( 2 ), [Zn(HNCP)(1, 3‐BDC)(H₂O)₂]_n ( 3 ), and {[Zn(HNCP)(5‐OH‐1, 3‐BDC)(H₂O) · H₂O}_n ( 4 ) were synthesized under hydrothermal conditions. Compounds 1 – 4 were determined by elemental analyses, IR spectroscopy, and single‐crystal and powder X‐ray diffraction. Compounds 1 and 2 are isomorphous, presenting a 4‐connected uninodal (4, 4)‐sql 2D framework with threefold interpenetration, which are further extended into the three‐dimensional (3D) supramolecular architecture through π ··· π stacking interactions between the aryl rings of 5‐NO₂‐1, 3‐BDC. Compared to compound 1 , 3 is obtained by using different reaction temperatures and metal‐ligand ratios, generating a 3D framework with –ABAB– fashion via π ··· π stacking interactions. Compound 4 is a 1D chain, which is further extended into a 3D supramolecular net by hydrogen bonds and π ··· π stacking interactions. The thermogravimetric and fluorescence properties of 1 – 4 were also explored.     

Four Metal Complexes Based on Bulky Imidazole Ligands: Solvothermal Syntheses,Crystal Structures,and Fluorescence Properties

In order to explore the influences of (de‐)protonation of the imidazole ring on the structural diversity of the resulting complexes, the imidazole‐based ligands 4, 5‐diphenylimidazole (Hdpi) and 1H‐phenanthro[9, 10‐d]imidazole (Hpi) were utilized as bulky building blocks to construct four complexes by solvothermal reactions, i.e. [Ag(Hdpi)₂](NO₃) · (H₂O) ( 1 ), [Cu(dpi)]_∞ ( 2 ), [Cu(Hpi)(NO₃)]_∞ ( 3 ), and [(H₂pi)(NO₃)] · H₂O ( 4 ). In complex 1 , two Hdpi ligands adopt a monodentate pattern and coordinate with one Ag^I ion to form a mononuclear unit, which is further connected by hydrogen bonds into a 1D supramolecular helix. The deprotonated dpi ligand of 2 acts in bidentate mode, and bridges Cu^I ions to afford a 1D chain. In 3 , the NO₃^– ion, acts as a monodentate bridging ligand and joins Cu^I ions to generate a 1D chain. The Hpi ligand employs a monodentate mode to bond with Cu^I ions of the 1D chain. 4 is protonated and two H₂pi nitrogen atoms are free of coordination. Interestingly, hydrogen bonds among the NO₃^– ion, the H₂pi ligand, and the water molecule yield a macro ring R⁴₄(14). The resulting structural diversity reveals that the (de‐)protonation of imidazole ring directly steers the coordination number of ligand, and thus causes a significant effect on the structure, especially the dimensionality. Furthermore, the solid‐state fluorescence properties of the free ligands and compounds 1 – 4 were studied at room temperature.     

Asymmetric Construction of Spirooxindoles by Organocatalytic Multicomponent Reactions Using Diazooxindoles

The first highly diastereo‐ and enantioselective multicomponent reaction of diazooxindoles, nitrosoarenes, and nitroalkenes using a newly developed hydrogen‐bond catalyst has been successfully developed for the efficient construction of a series of spirooxindole derivatives with excellent functional‐group tolerance. Spirooxindoles are formed in excellent yields and stereoselectivities, and the method represents an unprecedented approach for trapping the active intermediate with a nitroalkene to form biologically important compounds having three contiguous stereogenic centers with excellent asymmetric induction.