Cyclotriphosphazenes as scaffolds for the synthesis of metallomesogens

Jiménez, Josefina (Universidad de Zaragoza) ; Sanz, José Antonio ; Serrano, José Luis (Universidad de Zaragoza) ; Barberá, Joaquín (Universidad de Zaragoza) ; Oriol, Luis (Universidad de Zaragoza)

Resumen: (Amino)cyclotriphosphazenes have been used as new scaffolds for the synthesis of silver(I) metallomesogens. Two cyclotriphosphazenes, [N3P3(NHCy)6] (phos-1) and nongem-trans-[N3P3(NHCy)3(NMe2)3] (phos-2), were reacted with the silver complex having a pro-mesogenic ligand, [Ag(OTf)L] (L = CNC6H4{OC(O)C6H2(3, 4, 5-(OC10H21)3)}-4; OTf = OSO2CF3), in different molar ratios, 1:1, 1:2, or 1:3, to give two series of cationic metallophosphazenes, [N3P3(NHCy)6{AgL}n](TfO)n (phos-1.n) and nongem-trans-[N3P3(NHCy)3(NMe2)3{AgL}n](TfO)n (phos-2.n) with n = 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 n 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.

Idioma: Inglés

DOI: 10.1021/acs.inorgchem.0c00124

Año: 2020

Publicado en: Inorganic Chemistry 59, 7 (2020), 4842-4857
ISSN: 0020-1669

Factor impacto JCR: 5.165 (2020)

Categ. JCR: CHEMISTRY, INORGANIC & NUCLEAR rank: 5 / 45 = 0.111 (2020) - Q1 - T1

Factor impacto SCIMAGO: 1.348 - Chemistry (miscellaneous) (Q1) - Physical and Theoretical Chemistry (Q1) - Inorganic Chemistry (Q1)

Financiación: info:eu-repo/grantAgreement/ES/DGA/E47-17R
Financiación: info:eu-repo/grantAgreement/ES/MINECO/MAT2017-84838-P

Tipo y forma: Article (PostPrint)

Área (Departamento): Área Química Inorgánica (Dpto. Química Inorgánica)
Área (Departamento): Área Química Orgánica (Dpto. Química Orgánica)