Substituent Effects on the Structures of Silver Complexes with Monoazatrithia-12-Crown-4 Ethers Bearing Substituted Aromatic Rings

New 4‘-methoxybenzyl-, 4‘-methylbenzyl-, benzyl-, 3‘,5‘-difluorobenzyl-, 3‘,5‘-dichlorobenzyl-, and 4‘-nitrobenzyl-armed monoazatrithia-12-crown-4 ethers were prepared by the reductive amination of monoazatrithia-12-crown-4
with the appropriate benzenecarbaldehyde in the presence of NaBH(OAc)3. Cold electrospray ionization mass
spectrometry and X-ray crystallography show that silver complexes with armed monoazatrithia-12-crown-4 ethers
bearing aromatic side arms with electron-donating groups or electron-withdrawing groups are coordination polymers
and trimers, respectively. The structures of the silver complexes were strongly dependent on the strength of the
CH···π interactions, which are controlled by substituent effects on the aromatic side arms.