A new type of chiral tertiary amine ligand was designed and derived from l-proline and (R)-BINOL. These new chiral ligands chelated with Cu(II) showed highly catalytic efficiency in enantioselective Henry reactions. Excellent yields (up to 99%) and high enantioselectivities (up to 96% ee) were achieved for aromatic, hetero-aromatic and aliphatic aldehyde substrates, without an additional base additive or the need for air or moisture exclusion.(S)-1-(2-((R)-3H-Dinaphtho[2,1-c:1′,2′-e]azepin-4(5H)-yl)ethyl)-N-butylpyrrolidine-2-carboxamideC33H37N3O[α]D25 = −248.0 (c 0.51, CH2Cl2)Absolute configuration: (S,R)(S)-1-(2-((R)-3H-Dinaphtho[2,1-c:1′,2′-e]azepin-4(5H)-yl)ethyl)-N-(tert-butyl)pyrrolidine-2-carboxamideC33H37N3O[α]D25 = −222.8 (c 0.5, CH2Cl2)Absolute configuration: (S,R)(S)-1-(2-((R)-3H-Dinaphtho[2,1-c:1′,2′-e]azepin-4(5H)-yl)ethyl)-N-cyclohexylpyrrolidine-2-carboxamideC35H39N3O[α]D25 = −229.4 (c 0.5, CH2Cl2)Absolute configuration: (S,R)(S)-1-(2-((R)-3H-Dinaphtho[2,1-c:1′,2′-e]azepin-4(5H)-yl)ethyl)-N-phenylpyrrolidine-2-carboxamideC35H33N3O[α]D25 = −297.4 (c 0.5, CH2Cl2)Absolute configuration: (S,R)(S)-1-(2-((R)-3H-Dinaphtho[2,1-c:1′,2′-e]azepin-4(5H)-yl)ethyl)-N-(naphthalen-1-yl)pyrrolidine-2-carboxamideC39H36N3O[α]D31 = 239.0 (c 0.51, CH2Cl2)Absolute configuration: (S,R)(R)-4-(2-(Pyrrolidin-1-yl)ethyl)-4,5-dihydro-3H-dinaphtho[2,1-c:1′,2′-e]azepineC28H28N2[α]D25 = +63.7 (c 0.19, CH2Cl2)Absolute configuration: (R)(S)-1-(2-(Isoindolin-2-yl)ethyl)-N-(naphthalen-1-yl)pyrrolidine-2-carboxamideC25H28N3O[α]D25 = −79.4 (c 0.51, CH2Cl2)Absolute configuration: (R)

We report the synthesis and characterization of a series of novel C3h-symmetric 2,4,6-tris(2-hydroxyphenyl)-1,3,5-triazine (THPT) derivatives. These compounds possess an interesting intramolecular hydrogen bonding pattern, which leads to the planarization between the triazine ring and the pendant aryl groups. The enhanced π-stacking interaction, resulting from the planarization, facilitates the column formation. Two of them exhibit a columnar hexagonal phase (Colh) over a wide temperature range induced by strong intramolecular hydrogen bonds.

Two superaromatic terpyridine ligands (1 and 2) incorporating a corannulene unit at the 4′-position are reported. The optical and metal sensing properties of both ligands were investigated by the naked eye, and UV-vis and fluorescence spectroscopy in this work. In 1, the corannulene motif is directly connected to the 4′-phenylterpyridine domain, while in 2, the corannulene motif and the 4′-phenylterpyridine domain are separated by an acetylene linker. Both 1 and 2 can work as chemosensors for metal ions and display different optical responses to various metal ions. It is shown that both ligands exhibit a colorimetric sensing ability for Fe2+ through an obvious color change from colorless to magenta, and this color change can be observed easily by the naked eye. The addition of Fe2+ also leads to significant changes in the absorption spectra of the ligands. A characteristic red shift in the emission spectra is observed in the presence of Zn2+, which facilitates the discrimination of Zn2+ from other metal ions. In addition, density functional theory (DFT) and time-dependent-density functional theory (TD-DFT) calculations were performed and shown to be consistent with the observed experimental results.

Two superaromatic terpyridine ligands (1 and 2) incorporating a corannulene unit at the 4′-position are reported. The optical and metal sensing properties of both ligands were investigated by the naked eye, and UV-vis and fluorescence spectroscopy in this work. In 1, the corannulene motif is directly connected to the 4′-phenylterpyridine domain, while in 2, the corannulene motif and the 4′-phenylterpyridine domain are separated by an acetylene linker. Both 1 and 2 can work as chemosensors for metal ions and display different optical responses to various metal ions. It is shown that both ligands exhibit a colorimetric sensing ability for Fe2+ through an obvious color change from colorless to magenta, and this color change can be observed easily by the naked eye. The addition of Fe2+ also leads to significant changes in the absorption spectra of the ligands. A characteristic red shift in the emission spectra is observed in the presence of Zn2+, which facilitates the discrimination of Zn2+ from other metal ions. In addition, density functional theory (DFT) and time-dependent-density functional theory (TD-DFT) calculations were performed and shown to be consistent with the observed experimental results.