Investigating the geometrical preferences of a flexible benzimidazolone-based linker in the synthesis of coordination polymers

研究柔性苯并咪唑酮基连接基团在配位聚合物合成中的几何偏好

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Abstract

A series of new group 2 coordination polymers, MgL ={MgL(H(2)O)(DMF)(0.75)}(∞), CaL = {CaL(DMF)(2)}(∞), SrL = {SrL(H(2)O)(0.5)}(∞) and BaL = {BaL(H(2)O)(0.5)}(∞), were synthesized using a flexible benzimidazolone diacetic acid linker (H(2)L) in which the two carboxylic acid binding sites are connected to a planar core via {-CH(2)-} spacers that can freely rotate in solution. In a 'curiosity-led' diversion from group 2 metals, the first row transition metal salts Mn(2+), Cu(2+) and Zn(2+) were also reacted with L to yield crystals of MnL = {MnL(DMF)(H(2)O)(3.33)}(∞), Cu(3)L(2) = {Cu(3)L(2)(DMF)(2)(CHO(2))(2)}(∞) and ZnL = {ZnL(DMF)}(∞). Crystal structures were obtained for all seven materials. All structures form as two-dimensional sheets and contain six-coordinate centres, with the exception of ZnL, which displays tetrahedrally coordinated metal centres, and Cu(3)L(2) , which contains square planar coordinated metal centres and Cu paddle-wheels. In each structure, the linker adopts one of two distinct conformations, with the carboxylate groups either cis or trans with respect to the planar core. All materials were also characterized by powder X-ray diffraction and thermogravimetric analysis.

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