Three-dimensional metal azide coordination polymers with amino carboxylate coligands: synthesis, structure, and magnetic properties.
The reaction of M(II) ions with azido ligands in the presence of different amino carboxylic acids gave four three-dimensional metal-azido coordination polymers, [Mn(3,5-daba)(N(3))](n) (1), [Cd(3,5-daba)(N(3))](n) (2; 3,5-daba = 3,5-diaminobenzoate), [Mn(4-aba)(N(3))](n) (3; 4-aba = 4-aminobenzoate), and [Cu(2)(gly)(2)(N(3))(2)](n) (4; gly = glycinate), which display different topological structures. Polymers 1 and 2 present 4,6-connected 3D networks with different Schlafli symbols. However, 3 and 4 feature an unprecedented trinodal 3,6-connected network with the Schlafli symbol (4(2).6)(4.6(2))(4(3).6(6).8(6)) and an unusual 4-connected 3D net with the Lonsdaleite (hexagonal diamond) topology, respectively. Magnetic susceptibility measurements revealed dominant antiferromagnetic couplings for 1 and 3 and an overall dominant ferromagnetic coupling for 4, which presents metamagnetic behavior with a magnetic phase transition at a critical temperature of 6 K and a transition field of ca. 6030 Oe. The results demonstrate that the EE azido and syn-anti carboxylato bridges in our cases induce an antiferomagnetic interaction, and the anti-anti carboxylato bridge in 4 mediates a ferromagnetic interaction. The magnetic interaction through the EO azido bridge in 3 and 4 has a dependence on the value of the M-N-M bond angle.
Chen
Zi-Lu
ZL
School of Chemistry and Chemical Engineering, Guangxi Normal University, Guilin 541004, China.
Jiang
Chun-Fang
CF
Yan
Wei-Hong
WH
Liang
Fu-Pei
FP
Batten
Stuart R
SR
D001386:Azides / Q000737:chemistry*; D002264:Carboxylic Acids / Q000737:chemistry*; D018360:Crystallography, X-Ray; D008024:Ligands; D008280:Magnetics; D019216:Metals, Heavy / Q000737:chemistry*; D008958:Models, Molecular; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry; D011108:Polymers / Q000138:chemical synthesis / Q000737:chemistry; D013696:Temperature
D001386:Azides; D002264:Carboxylic Acids; D008024:Ligands; D019216:Metals, Heavy; D009942:Organometallic Compounds; D011108:Polymers