Syntheses and characterization of various supramolecular compounds from the self-assembly of nickel(II) hexaaza macrocyclic complex with carboxylic acid derivatives

详细信息    查看全文

• 作者：Jong Won Shin ; Dae-Woong Kim ; Dohyun Moon ; ^{dmoon@postech.ac.kr" class="auth_mail" title="E-mail the corresponding author}
• 关键词：1-D zigzag coordination polymer ; Supramolecular structure ; Antiferromagnetic interaction ; π&ndash ; π interaction ; Hydrogen bonding interaction
• 刊名：Polyhedron
• 出版年：2016
• 出版时间：17 February 2016
• 年：2016
• 卷：105
• 期：Complete
• 页码：62-70
• 全文大小：3480 K

文摘

The supramolecular compounds [Ni(C₁₆H₃₈N₆)(2,7-NDC)] (1), [Ni(C₁₆H₃₈N₆)(H₂O)₂] [Ni(C₁₆H₃₈N₆)(1,3,5-BTC)₂] (2), and [Ni(C₁₆H₃₈N₆)(nicotinate)₂] (3) were prepared via self-assembly of a nickel(II) azamacrocyclic complex containing butyl pendant groups, [Ni(C₁₆H₃₈N₆)(ClO₄)₂], with 2,7-naphthalenedicarboxylic acid (2,7-NDC), 1,3,5-benzenetricarboxylic acid (1,3,5-BTC), and nicotinic acid, respectively. These compounds were characterized by elemental analysis, infrared spectroscopy, magnetic measurement and single crystal X-ray diffraction. In 1, the nickel(II) azamacrocyclic complex links two 2,7-NDC²⁻ ligand at the axial position and each 2,7-NDC²⁻ ligand binds two adjacent nickel(II) azamacrocylic units with syn–syn and syn–anti orientations to form a zigzag 1-D chain structure. The zigzag 1-D chain tends to interact via offset face-to-face π–π interactions with adjacent 1-D chains, which leads to a 2-D supramolecular network. Compound 1 exhibits very weak antiferromagnetic interactions through the bridged 2,7-NDC²⁻ ligand within the 1-D zigzag chains (g = 2.11 and J/κ_B = −0.29 cm⁻¹). Compound 2 consists of two nickel(II) azamacrocyclic cation units and one nickel(II) azamacrocylic anion unit. Each nickel(II) ion in the cation and anion units is coordinated with four nitrogen atoms of the azamacrocyclic ligand in the equatorial plane, and two oxygen atoms from the water molecules or BTC³⁻ ligands at the axial positions, to display a distorted octahedral geometry. The cation and anion units form intermolecular hydrogen bonds, giving rise to a 3-D supramolecular structure. In 3, the coordination environment around the nickel(II) ion has a distorted octahedral geometry via coordination with four nitrogen atoms of the azamacrocyclic ligand in the equatorial plane, and two nicotinate anions at the axial positions and intramolecular hydrogen bonding interactions between the amine groups and nicotinate anions stabilize the molecular structure.