Supramolecular structural influences from remote functionality in coordination complexes of 4-picolylamine ligands

Adamantane-type clusters: compounds with a ubiquitous architecture but a wide variety of compositions and unexpected materials properties

“…[401,[442][443][444] Anionic clusters can be generated, when not all chloride atoms are substituted by a ligand during the reaction. [416,436] When no coordinating ligand is present, tetraanions [µ4-O(CuCl)4Cl6] 4− (in 766-772, Figure 16) can be isolated readily with different counterions. [445][446][447][448][449][450][451] While not as extensively studied, the Br homologs [µ4-O{Cu(L)}4Br6] (773-779, Figure 16) [394,432,[452][453][454][455] were found to be achievable in a similar way by using the appropriate CuBrx salts.…”

“…[µ4-O{Cu(MeOH)}4Cl6] (737), urea / THF, 2 h Q [444] [4-phenylimidazolium][µ4-O{Cu(4-phenylimidazole)}3{CuCl}Cl6] (764) CuCl2•2H2O, 4-phenylimidazole / MeOH, 45 min C [416] [µ4-O(Cu{N-(α-4-picolyl)morpholine})2(Cu{N-(α-4picolyl)morpholinium})(CuCl)Cl6] (765) CuCl2•2H2O, N-(α-4-picolyl)morpholine / MeCN, H2O C [436] [Me4N]4 CuBr2, CuO, Py / H2O, 100 °C, C [452] [µ4-O{Cu(nicotine)}4Br6] (774)…”

“…401,[442][443][444] Anionic clusters can be generated when not all chloride atoms are substituted by a ligand during the reaction. 416,436 When no coordinating ligand is present, tetraanions [m 4 -O(CuCl) 4 Cl 6 ] 4− (in 766-772, Fig. 16) can be isolated readily with different counterions.…”

“…They were isolated after an addition of simple CuCl x to L in the presence of ambient air, hydroxide or CuO. 385–436 In some of those cases, the oxygen source could not be determined and is most likely a H 2 O or O 2 impurity in the reaction, or stems from decomposition of the solvent. A deviating synthetic strategy uses oligomeric [LCuCl] x complexes already containing the desired ligand, which rearrange to the desired product.…”