Air and moisture stable covalently-bonded tin(ii) coordination polymers

Abstract

Four covalently-bonded tin(ii) coordination polymers, (1)-(4), were hydrothermally prepared in aqueous alkaline media by the reactions of SnSO4 with 1,2,4,5-benzenetetracarboxylic acid (1), 1,3,5-benzenetricarboxylic acid (2), 4-hydroxypyridine-2,6-dicarboxylic acid (3), and 1,3,5-cyclohexanetricarboxylic acid (4). All products were structurally authenticated by single-crystal X-ray diffraction, and the number of different tin centres and their oxidation states were confirmed by 119Sn Mössbauer spectroscopy. In addition, the comparison between experimental and simulated X-ray powder diffraction patterns confirmed the authenticity of the samples. Our crystallographic results for (1)-(4) show that the Sn(ii) centres are tetracoordinated and exhibit distorted disphenoidal geometries, corroborating the presence of one stereochemically active lone electron pair at each metal site. Products (1) and (2) display bi-dimensional polymeric structures, (3) exhibits a one-dimensional architecture, whereas (4) shows a remarkable three-dimensional coordination network. Hirshfeld surface and supramolecular analyses for the repeating units of (1)-(4) were also performed in order to identify structurally important non-covalent interactions.

Recent advances in structures and applications of coordination polymers based on cyclohexanepolycarboxylate ligands

“…40 When replaced by tin which is bound to four oxygen atoms from different carboxylate groups in distorted disphenoidal geometry, the metal atoms are bridged by 1,3,5-CHTC in coordination mode IV into a 3D framework, [Sn 3 (1,3,5-CHTC) 2 ]. 41…”

Estanho: Um Metal Estratégico Ontem E Hoje

“…24 Mas curiosamente, na última década surgiram alguns polímeros de coordenação de Sn(II) com alta estabilidade química e térmica, contrariando a tendência observada nos primeiro compostos de Sn(II) sintetizados anos antes. 25 Dentre…”

“…56,57 Recentemente alguns exemplos interessantes de polímeros de coordenação de Sn(II) enriqueceram a química desse cátion, sintetizados através de reações hidrotérmicas em meio alcalino, entre ácidos carboxílicos e SnSO 4 . 25…”

Imparting Superhydrophobicity to Porphyrinic Coordination Frameworks Using Organotin

“…[26][27][28] Tin has also been used to fabricate MOFs, but only a few examples have been reported to date, most of which are pore-free structures. [29][30][31][32][33][34][35][36][37] As opposed to the introduction of hydrophobic linkers or via PSM by fluoroalkyl chains or other hydrophobic groups on the metal-oxo nodes, theoretically, organotin species could be introduced directly into the SBUs of MOFs to improve the environment of their inner cavities.…”