Cyclotriphosphazenes as Scaffolds for the Synthesis of Metallomesogens.

Inorg Chem

Departamento de Quı́mica Orgánica, Facultad de Ciencias - Instituto de Ciencia de Materiales de Aragón (ICMA), Universidad de Zaragoza-CSIC, Zaragoza 50009, Spain.

Published: April 2020

AI Article Synopsis

  • - The study explores the synthesis of new silver(I) metallomesogens using (amino)cyclotriphosphazenes as scaffolds, resulting in two series of cationic metallophosphazenes via reactions with a silver complex at various molar ratios.
  • - The resulting compounds were characterized through spectroscopy, confirming that silver fragments coordinated to nitrogen atoms in the phosphazene structure, with the number of coordinations dependent on the molar ratios used.
  • - Despite bulky substituents on the nitrogen atoms, the metallophosphazenes demonstrated mesomorphism at room temperature, forming a columnar hexagonal mesophase as shown by optical microscopy and X-ray diffraction, leading to a proposed model for their

Article Abstract

(Amino)cyclotriphosphazenes have been used as new scaffolds for the synthesis of silver(I) metallomesogens. Two cyclotriphosphazenes, [NP(NHCy)] () and [NP(NHCy)(NMe)] (), were reacted with the silver complex having a pro-mesogenic ligand, [Ag(OTf)L] (L = CNCH{OC(O)CH(3,4,5-(OCH))}-4; OTf = OSOCF), in different molar ratios, 1:1, 1:2, or 1:3, to give two series of cationic metallophosphazenes, [NP(NHCy){AgL}](TfO) () and [NP(NHCy)(NMe){AgL}](TfO) () with = 1, 2, or 3. The chemical structure of these compounds, deduced from spectroscopic techniques, was in accordance with coordination of the silver fragments "AgL" to nitrogen atoms of the phosphazene ring, whereby their number depends on the molar ratio used. Despite the presence of the bulky substituents on the core N atoms, cyclotriphosphazenes coordinated to three "AgL" units exhibited mesomorphism at room temperature. The mesophase was characterized as columnar hexagonal according to the optical microscopy and X-ray diffraction studies. A model based on an intermolecular association in pairs of the metallocyclotriphosphazenes having three AgL units has been proposed in order to explain the mesomorphic columnar arrangement in these materials. Starting silver complex, [Ag(OTf)L], also exhibited a columnar hexagonal mesophase at room temperature.

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Source
http://dx.doi.org/10.1021/acs.inorgchem.0c00124DOI Listing

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