Metal ion determined self-assembly using terpyridine building blocks

Abstract

Due to the dynamic reversibility of coordination-driven force, the structures of metallo-cages are sensitive to many stimulus, including ligand geometry, temperature, concentration, anions, pH, light, and so on. Among them,...

Metal-ion-determined geometrical configurations of metallo-cages with different emission properties

“…[29][30][31] In our previous work, the effect of different metal ions on the compositions of metallo-cages has been explored. 32 However, the more sophisticated situation in which metal ions induce geometric configuration variations has rarely been studied.…”

Construction of 1,3,5-Triazine-Based Prisms and Their Enhanced Solid-State Emissions

“…In nature, the coordination of metal ions with organic substrates has been exploited to create various functional compounds, such as chlorophyll, vitamin B 12 , hemoglobin, etc. Compared to other weak noncovalent interactions, coordination bonds are advantageous in terms of their directionality and predictability. − Inspired by nature, chemists have utilized coordination-driven self-assembly strategies to construct discrete architectures from two-dimensional (2D) rings to three-dimensional (3D) cages with precise sizes and shapes, − which have applications in areas such as catalysis, cancer treatment, and optical materials; , among these architectures, 2,2′:6′,2″-terpyridine (tpy) as a building block has gained widespread attention owing to its remarkable binding ability to different transition-metal ions. ,− Compared to 2D rings, 3D nanocages demonstrate promising applications for anion recognition, − C 60 encapsulation, − and controlled release − because of their regular configuration with fixed-size cavities that can selectively encapsulate guest molecules …”

“…1 H NMR (400 MHz, Chloroform-d) δ 8.81 (d, J = 8.1 Hz, 6H, Ph-H j ), 8.74 (s, 6H, tpy-H 3 ′ ,5 ′), 8.69 (dd, J = 4.8, 1.6 Hz, 6H, tpy-H 6,6 ″), 8.65 (d, J = 8.0 Hz, 6H, tpy-H 3,3 ″), 7.87−7.81 (m, 18H, tpy-H 4,4 ″, Ph-H i , and Ph-H a ), 7.62 (d, J = 8.0 Hz, 6H, Ph-H h ), 7.54−7.47 (m, 12H, Ph-H c , Ph-H d , Ph-H e , and Ph-H f ), 7.36 (d, J = 8.0 Hz, 6H, Ph-H b ), 7.31 (dd, J = 7.7, 4.1 Hz, 12H, tpy-H 5,5 ″, and Ph-H g ). 13 Synthesis of Ligand LB. A mixture of 2,4,6-tris(4-bromophenyl)-1,3,5-triazine (50 mg, 0.03 mmol), compound 2 (94.5 mg, 0.12 mmol), and Pd(PPh 3 ) 2 Cl 2 (3.5 mg, 0.005 mmol) was added in 100 mL Schlenk flask.…”

“…1 H NMR (400 MHz, Chloroform-d) δ 8.81 (d, J = 8.1 Hz, 6H, Ph-H h ), 8.74 (s, 6H, tpy-H 3 ′ ,5 ′), 8.70 (d, J = 4.9 Hz, 6H, tpy-H 6,6 ″), 8.65 (d, J = 8.0 Hz, 6H, tpy-H 3,3 ″), 7.88−7.80 (m, 18H, tpy-H 4,4 ″, Ph-H g , and Ph-H a ), 7.61 (d, J = 8.0 Hz, 6H, Ph-H f ), 7.36−7.28 (m, 18H, tpy-H 5,5 ″, Ph-H b , and Ph-H e ), 7.03 (d, J = 1.7 Hz, 6H, Ph-H c , and Ph-H d ), 4.12 (q, J = 6.1 Hz, 12H, Alkyl-H i , and Alkyl-H i' ), 1.92−1.85 (m, 12H, Alkyl-H j , and Alkyl-H j' ), 1.53 (s, 12H, Alkyl-H k , and Alkyl-H k' ), 1.41−1.34 (m, 24H, Alkyl-H l , Alkyl-H m , Alkyl-H l' , and Alkyl-H m' ), 0.95−0.90 (m, 18H, Alkyl-H n , and Alkyl-H n' ). 13 Synthesis of Complex SA. To a solution of ligand LA (6.0 mg, 3.56 μmol) in CHCl 3 (3 mL), a solution of Zn(NO 3 ) 2 •6H 2 O (1.6 mg, 5.34 μmol) in MeOH (3 mL) was added, and then the mixture was stirred at 50 °C for 12 h. After cooling to room temperature, excess NH 4 PF 6 (44 mg) was added to generate an orange precipitate (7.3 mg, 92%).…”