Rapid and scalable synthesis of chiral porphyrin cage compounds

Molecular motor-functionalized porphyrin macrocycles

“…To be able to connect 8 to a porphyrin cage compound via click chemistry, the latter needed to be equipped with an azide functionality. To this end, free base porphyrin cage compound H 2 1 26 , 27 was regioselectively mononitrated at one of its xylylene sidewalls via our recently developed procedure 28 to afford H 2 9 (50–75%). This compound was subsequently reduced to monoamino cage H 2 10 with stannous chloride and HCl 29 .…”

“…This observation is important in the sense that a manganese(III) derivative of Zn2 will be used as photo-switchable catalyst in which the motor moiety acts as the switching unit. In a last control experiment, we examined the properties of motor 8 in the presence of the non-luminescent and diamagnetic compound Ni1 26 (Table 1 , entry 5). Both the t 1/2 values and the PSS ratio were now found to be in the same range as those observed for motor 8 , which supports the aforementioned back-excitation effect displayed by luminescent Zn1 .…”

Double Porphyrin Cage Compounds

“…Compound 7 was synthesized according to a literature procedure. [9] Figure 9. Carbon, proton, and nitrogen numbering of 5-(5-bromo-2-methoxyphenyl)-10,15,20-tris(2-methoxyphenyl) porphyrin 5 (left) and the double cage compounds M 2 C n DC (M = 2H or Zn, n = 3, 5 or 11) (right) used for all NMR analyses.…”

“…3H,36,42),3H,35,41),3H,37,43), 3.61-3.51 (m, 9H, OMe-46,47,48), -2.89 (s, 2H, NH); 13 C{ 1 H}-NMR (CDCl 3 , 126 MHz): ∂ 159. 38,44), 149.00-144.00 (broad,5,7,10,12,15,17,20),34,40),33,39),4,8,9,13,14,18,19),36,42),35,41),11,16), 111.05-110.81 (ArC-31,37,43), 104.40 (ArC-1), 55.81 (OMe-46,47,48); UV/Vis (CHCl 3 ): λ/nm (log (ε/M -1 cm -1 )) 413 (5.74), 508 (4.25); Accurate mass: m/z 629.25449 [M + H] + ; calcd. for C 41 H 33 N 4 O 3 : 629.25526.…”

“…The crude product was purified by silica gel column chromatography using DCM/n-heptane (50:50 going to 75:25, (v/v)) as an eluent to yield 4 (467.7 mg, 0.66 mmol, 100 %) as a purple solid containing 3 atropisomers. 1 H-NMR (CDCl 3 , 500 MHz): ∂ 9.60 (d,2H,19,J = 4.8 Hz),8.80 (bs,2H,18),8.68 (bs,4H,9,13,14), 8. 3H,34,40),3H,36,42),3H,35,41),3H,37,43),9H,47,48), -2.63 (s, 2H, NH); 13 C{ 1 H}-NMR (CDCl 3 , 126 MHz): ∂ 159.…”