Anion Tuning of Cu(II)/4,4′‐Bi‐1,2,4‐Triazole Coordination Polymers

Abstract Nine Cu II coordination compounds based on 4,4′‐bi‐1,2,4‐triazole ( btr ), [Cu 2 ( N‐btr ) 2 (OAc) 4 ] · 4H 2 O ( 1 ), [Cu( N1,N1′‐btr ) 2 (H 2 O) 2 ][CdBr 4 (H 2 O)] · 3H 2 O ( 2 ), [Cu( N1,N1′‐btr ) 2 (H 2 O) 2 ]S 2 O 6 · 4H 2 O ( 3 ), [Cu( N1,N1′‐btr ) 2 (H 2 O) 2 ](NO 3 ) 2 · 2H 2 O ( 4 ), [Cu 2 ( N1,N1′‐btr ) 2 (μ 3 ‐btr ) 2 (NO 3 ) 2 ](NO 3 ) 2 · 2H 2 O ( 5 ), [Cu( N1,N1′ ‐ btr ) 2 (DMF) 2 ](NO 3 ) 2 · 2C 2 H 5 OH ( 6 ), [Cu( N1,N1′‐btr ) 3 ](CF 3 CO 2 ) 2 ( 7 ), [Cu( N1,N1′ ‐ btr ) 2 ( N ‐ btr ) 2 ](CCl 3 CO 2 ) 2 · 5H 2 O ( 8 ), [Cu 3 (μ 2 ‐OH) 2 (μ 4 ‐btr )(μ 3 ‐btr ) 2 ( N1,N1′‐btr )(H 2 O)(CF 3 CO 2 )](CF 3 CO 2 ) 3 · 4H 2 O ( 9 ), were synthesized by reaction of btr with the corresponding Cu II salts in aqueous or DMF/ethanol solution and their structures were established with single X‐ray diffraction. The coordination behavior of btr , which changes from simple monodentate, to N1,N1′ ‐bi‐, tri‐ and tetradentate binding modes, and the influence of the counteranions lead to a structural variety of the coordination compounds, ranging from molecular “Chinese lanterns” of type 1 , through 2D square grids ( 2 – 4 , 6 , 8 ) and 3D octahedral networks ( 7 ), to 3D eight‐connected frameworks ( 5 , 9 ) that based on the dinuclear [Cu 2 ( trz ) 2 ] 4+ and linear trinuclear [Cu 3 (μ 2 ‐OH) 2 (H 2 O) 2 ] 4+ units as nodes.