Syntheses, Crystal Structures and NBO Calculation of Two New Zinc(II) Coordination Polymers

• Published in: Journal of chemical crystallography 2020-06, Vol.50 (2), p.155-163
• Main Authors: Li, Xiu-Mei, Wang, Zhi-Tao, Valtchev, Valentin, Fang, Qian-Rong, Pan, Ya-Ru
• Format: Article
• Language: English
• Subjects: Acetic acid; Chemistry; Chemistry and Materials Science; Coordination polymers; Crystal structure; Crystallography and Scattering Methods; Fluorescence; Hydrogen bonding; Infrared spectroscopy; Inorganic Chemistry; Mathematical analysis; Organometallic Chemistry; Original Paper; Photoluminescence; Physical Chemistry; Polymers; Single crystals; Stacking; Synthesis; X-ray diffraction; Zinc; Zinc coordination
• ISSN: 1074-1542; 1572-8854
• DOI: 10.1007/s10870-019-00807-3

Two new Zn(II) coordination polymers based on bis(imidazol), namely, [Zn(hba) 2 (bib)] n (1) and [Zn(NAA)(bib) 1.5 ] n ·nNO 3 − ·3nH 2 O (2) (Hhba  =  3-hydroxybenzoic acid, HNAA = 1-naphthyl acetic acid, bib = 1,4-bis(imidazol-1-yl)-butane) have been successfully synthesized under hydrothermal conditions. Their structures have been determined by single crystal X-ray diffraction analyses, elemental analyses, IR, TG and fluorescence spectrums. Complex 1 shows a one-dimensional zigzag chain structure. Complex 2 exhibits two-dimensional network structure. The intermolecular hydrogen bonding and π–π stacking interactions extend the complexes 1 and 2 into supramolecular architectures and play an important role in stabilizing complexes 1 and 2 . Furthermore, complex 1 exhibits intense blue luminescence and appears to be a good candidate for novel hybrid inorganic–organic photoactive materials, while no photoluminescent response was observed for complex 2 . In addition, we analyzed the Natural Bond Orbitals (NBO) of 1 and 2 using the PBE0/LANL2DZ method in the Gaussian 09 Program. The calculations showed the obvious covalent interaction between the coordinated atoms and Zn(II) ion. Graphic Abstract Two new Zn(II) coordination polymers based on bis(imidazol), namely, [Zn(hba) 2 (bib)] n (1) and [Zn(NAA)(bib) 1.5 ] n ·nNO 3 − ·3nH 2 O (2) have been successfully synthesized under hydrothermal conditions. Their structures have been determined by single crystal X-ray diffraction analyses, elemental analyses, IR, TG and fluorescence spectrum. Complex 1 shows a one-dimensional zigzag chain structure. Complex 2 exhibits two-dimensional network structure. The intermolecular hydrogen bonding and π–π stacking interactions extend the complex 1 and 2 into supramolecular architectures and play an important role in stabilizing complex 1 and 2 . In addition, we analyzed Natural Bond Orbital (NBO) of 1 and 2 in using the PBE0/LANL2DZ method built in Gaussian 09 Program. The calculation results showed the obvious covalent interaction between the coordinated atoms and Zn(II) ion.