Four isostructural lanthanide(III) coordination compounds based on a new N‐oxydic pyridyl naphthalenediimide ligand: synthesis and characterization. Issue 1 (14th December 2018)

• Record Type: Journal Article
• Authors: Xiang, Zheng; Shan, Yue-Bin; Li, Tao; Huang, Chang-Cang; Huang, Xi-He; Lin, Mei-Jin
• Is Part Of: Acta crystallographica. Volume 75:Issue 1(2019)
• Page Start: 38
• Page End: 45
• Publication Date: 2018-12-14
• Subjects: coordination polymer -- naphthalenediimide -- lanthanide -- crystal structure -- nine‐coordinate -- semiconductor; Crystallography -- Periodicals; Crystals -- Periodicals; 548.3
• DOI: 10.1107/S2053229618017357
• Languages: English
• ISSNs: 2053-2296

Abstract

Abstract : Four novel isostructural lanthanide(III) coordination polymers based on a novel N ‐oxydic pyridyl naphthalenediimide ligand were synthesized and their crystal structures analysed. One of them demonstrates potential as an indirect band gap semiconductor material. Abstract : Naphthalenediimides, an attractive class of electron‐deficient organic dyes with rich redox and photoredox properties, have been investigated extensively as building blocks for coordination networks or metal–organic frameworks in recent decades. However, most of the available work has focused on d ‐block metal cations rather than f ‐block lanthanide ions, whose complexes exhibit a large variability in coordination numbers. In this article, four coordination polymers composed of naphthalenediimides and lanthanide cations, namely catena ‐poly[[[tris(nitrato‐κ 2 O, O ′)lanthanide]‐bis{μ‐ N, N ′‐bis[(1‐oxidopyridin‐1‐ium‐3‐yl)methyl]‐1, 8:4, 5‐naphthalenetetracarboxdiimide‐κ 2 O : O ′}‐[tris(nitrato‐κ 2 O, O ′)lanthanide]‐μ‐ N, N ′‐bis[(1‐oxidopyridin‐1‐ium‐3‐yl)methyl]‐1, 8:4, 5‐naphthalenetetracarboxdiimide‐κ 2 O : O ′] methanol disolvate], {[Ln(C26 H16 N4 O4 )1.5 (NO3 )3 ]·CH3 OH} n, with Ln = Eu, 1, Gd, 2, Dy, 3, and Er, 4, have been successfully synthesized under hydrothermal conditions. Single‐crystal X‐ray diffraction analyses revealed that the four compounds are isomorphic and that each asymmetric unit contains one nine‐coordinated Ln centre, one and a half diimide ligands, three nitrate anions and one uncoordinated methanol molecule. In addition, each metal centre is surrounded by nine O atoms in a distorted tricapped trigonal–prismatic geometry. Two centres are bridged by two cis ligands to form a ring, which is further bridged by trans ligands to generate one‐dimensional chains. Neighbouring chains are stacked via π–π interactions between pyridine rings to give a two‐dimensional structure, which is stabilized by π–π interactions between naphthalene rings, forming the final three‐dimensional supermolecular network. Solid‐state optical diffuse‐reflectance spectral studies indicate that compound4 is a potential wide band gap semiconductor.