Anion-Dependent Self-Assembly of Silver(I) and Diaminotriazines to Coordination Polymers: Non-Covalent Bonds and Role Interchange between Silver and Hydrogen Bonds

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• 作者：Blanca R. Manzano ; Fe&#769 ; lix A. Jalo&#769 ; n ; M. Laura Soriano ; M. Carmen Carrio&#769 ; n ; M. Pilar Carranza ; Kurt Mereiter ; Ana M. Rodri&#769 ; guez ; Antonio de la Hoz ; Ana Sa&#769 ; nchez-Migallo&#769 ; n
• 刊名：Inorganic Chemistry
• 出版年：2008
• 出版时间：October 6, 2008
• 年：2008
• 卷：47
• 期：19
• 页码：8957-8971
• 全文大小：636K
• 年卷期：v.47,no.19(October 6, 2008)
• ISSN：1520-510X

文摘

New coordination polymers have been obtained by the self-assembly of silver salts AgX (X = BF₄, PF₆, CF₃SO₃) and 2,4-diamino-6-R-1,3,5-triazines L (R = phenyl and p-tolyl) of formulas AgLX (1−6). A complex of different stoichiometry, [Ag₃L₂(H₂O)(acetone)₂](BF₄)₃, 7 (R = phenyl), has also been synthesized. The three-dimensional structures of five compounds have been determined by X-ray diffraction studies. For the AgLX complexes, when X = BF₄ and R = phenyl or p-tolyl, chiral chains with alternating Ag and L are formed. The chains are cross-linked by the counteranions in a three-dimensional fashion through hydrogen bonds and weak Ag···F interactions giving rise to a structure with solvent-filled channels. Different and more compact structures have been found when the counteranion is CF₃SO₃ (OTf). When R = phenyl, sheets are formed which consist of [Ag₂(OTf)₂L₂] units with double triflate bridges and which contain columns of π−π stacked arenes. Hydrogen bonds connect the sheets. When AgOTf is used and R is p-tolyl, a different and unusual ladderlike structure is obtained in which the rungs are double asymmetric bridges consisting of the triflate groups bonded to Ag in κ²O,μ₂-O and κ¹O,μ₂-O fashion. The ladders are parallel to each other and are mutually linked by N−H···N hydrogen bonds to give a 3D architecture. A very similar ladderlike structure has been found for 7 but with a water molecule and a BF₄⁻ group acting as bridges. The role played by the hydrogen bonds in complex 6 to form the 3-D structure is played in 7 by [Ag(acetone)₂] fragments. The noncovalent interactions play an important role in the different solid-state 3D structures. The behavior of the new derivatives in solution has also been analyzed. A new species has been detected at low temperatures, and this exhibits restricted rotation of the phenyl ring.