Synthesis and Supramolecular Architectures of Dinuclear Metallacyclic Silver(I) and Zigzag‐Chain Copper(II) Complexes Bearing 2,6‐Pyridinediylbis(3‐pyridinyl)methanone

The reaction of 2,6‐pyridinediylbis(3‐pyridinyl)methanone (abbreviated as L ) with various silver(I) salts yielded a series of complexes, namely, [Ag 2 ( L ) 2 ](ClO 4 ) 2 ( 1 ), {[Ag 2 ( L ) 2 ](ClO 4 ) 2 } ∞ ( 2 ), {[Ag 2 ( L ) 2 ](NO 3 ) 2 } ∞ ( 3 ), {[Ag 2 ( L ) 2 ](C 2 F 5 CO 2 ) 2 } ∞ ( 4 ), {[Ag 2 ( L ) 2 ](C 3 F 7 CO 2 ) 2 } ∞ ( 5 ), and {[Ag 2 ( L ) 2 ](O 2 CC 3 F 6 CO 2 ) · 2H 2 O} ∞ ( 6 ), which exhibit a common dinuclear metallacyclic [Ag 2 ( L ) 2 ] 2+ skeleton that involves linear‐dicoordinate Ag I and μ 2 ‐ N , N ‐bridging L . Complex 2 is a polymorph of 1 obtained by the solvent‐medium tuning effect, and it has an {[Ag 2 ( L ) 2 ] 2+ } ∞ infinite‐chain structure. In complexes 3 – 6 , the argentophilic interaction plays an important role in connecting the [Ag 2 ( L ) 2 ] 2+ units to form a similar {[Ag 2 ( L ) 2 ] 2+ } ∞ chain structure to that in 2 , although the counteranions are markedly different. The copper(II) complex {[Cu 2 (CH 3 CO 2 ) 4 ( L )] · 2H 2 O} ∞ ( 7 ) exhibits a zigzag‐chain structure composed of an alternating arrangement of L and the Cu 2 (CH 3 CO 2 ) 4 paddlewheel cluster. In the supramolecular architectures of 1 – 7 , the counteranions engage in multiple noncovalent interactions, and the presence of unusual types such as O/F(anion) ··· π, O/F(anion) ··· C=O, and C=O ··· π are noted and discussed.