Molecular Networks Based on CN Coordination Bonds

This study examines the use of tetrahedral [E(O–C 6 X 4 –CN) 4 ] – anions (E = B, Al; X = H, F), which can be synthesized from the reaction of tetrahedral NaBH 4 /LiAlH 4 and HO–C 6 X 4 –CN, as anionic linkers for the generation of 2D and 3D crystalline coordination polymer networks. Such polymer networks were obtained by the connection of tetrahedral p ‐cyanophenoxy aluminate or borate linkers with monocationic metal centers such as Li + , Na + , Ag + , and Cu + . These studies are specifically focused on the synthesis, structure, and stability of such polymers. Additionally, the perfluorinated O–C 6 F 4 –CN linker was used to study electronic influences. Salts bearing the perfluorinated [E(O–C 6 F 4 –CN) 4 ] – anion decompose into E(O–C 6 F 4 –CN) 3 and [O–C 6 F 4 –CN] – , which is also observed when a Lewis acid such as B(C 6 F 5 ) 3 is added. Moreover, addition of B(C 6 F 5 ) 3 leads to the formation of molecular‐ion pairs because the cyano groups are now either completely or partly blocked. The structures of M[Al(O–C 6 H 4 –CN) 4 ] (M = Li, Ag, Cu), Na[B(O–C 6 H 4 –CN) 4 ], and Li[Al(O–C 6 F 4 –CN) 4 ] as well as of the decomposition products Na(O–C 6 F 4 –CN), (THF)Al[O–C 6 H 4 –CN · B(C 6 F 5 ) 3 ] 3 (THF = tetrahydrofuran), Na[(F 5 C 6 ) 3 B · O–C 6 H 4 –CN · B(C 6 F 5 ) 3 ], and Li[NC–C 6 F 4 –O–Al{O–C 6 F 4 –CN · B(C 6 F 5 ) 3 } 3 ] are discussed.