Synthesis of Shape‐Persistent Macrocycles with Three 1,8‐Diazaanthracene Units and Their Packing in the Single Crystal

Abstract

The synthesis of four shape-persistent macrocycles with three 1,8-diazaanthracene units each is reported (2,3 a-3 c). For two of them single crystals could be obtained and the structures in the crystal be solved. The structures reveal that macrocycle 2 self-dimerizes in the solid state; surprisingly it also forms a stable dimer in solution. The reason for this is seen in unusually efficient dispersion interactions as a consequence of the large contact areas in the dimer. All macrocycles are assessed as to their applicability in lateral polymerizations in the single crystal as well as in solution.

Room Temperature Synthesis of a Covalent Monolayer Sheet at Air/Water Interface Using a Shape-Persistent Photoreactive Amphiphilic Monomer

“…Chemical structures of anthracene- and 1,8-diazaanthracene-based monomers for two-dimensional polymer synthesis. ,, …”

Synthesis of Spiroligomer-Containing Macrocycles

“…A number of pre-organized macrocyclic scaffolds bearing well-defined structures have been developed, including calixarenes, 1-6 cyclodextrin, [7][8][9][10][11] resorcinarenes, [12][13][14][15][16][17] conjugated aromatic systems, [18][19][20][21][22][23] Schiff base macrocycles, 24-37 among others. [38][39][40][41][42][43][44][45][46][47][48] However, site-specifically incorporating multiple and diverse functional groups, such as catalytic groups or protein binding groups within these scaffolds is often challenging due the inherent symmetry of many of the most studied macromolecules.…”

“…The reaction was stirred under inert atmosphere for 24 hours until completion as indicated by LC-MS. The solvent was removed under vacuum and the residue was purified through reverse phase C18 column using 5-95% at 274 nm (C18 reverse phase, 30 mins, 5-95 % H 2 O/acetonitrile with 0.1 % formic acid): Tr= 23.5 mins. HRMS-ESI: m/z Calculated for C 90 H 86 N 12 O 16 (M + 2H)/2 + : 796.8231; found: 796.8251.…”

“…), 2×brine and dried over anhydrous Na 2 SO 4 . After filtration and removal of solvent under vacuum, the crude residue was purified by reverse phase C18 column using 5-95% H 2 O/acetonitrile gradient as eluting solvent to give pure di-alkene as white powder 42 (70 mg, 0.043 mmol, 59 % isolated yield). The di-alkene intermediate 42 was then subjected to the metathesis reaction as described in synthesis of macrocycle 38 to give macrocycle 44 with an 80 % isolated yield.…”

Ink‐Free Reversible Optical Writing in Monolayers by Polymerization of a Trifunctional Monomer: Toward Rewritable “Molecular Paper”

“…For synthetic reasons, however, it is not trivial to introduce a substituent at C* to monomer 1 . Gratifyingly, the structurally closely related monomer 2 , which carries a methyl group at the same position has recently been synthesized in our group . While there is far less literature for diazaanthracenes (DAA) than for A units and their derivatives, it seems that DAA units exhibit reactivity similar to A as far as cycloaddition and oxidation are concerned (Figure c,d).…”