Issue 37, 2022

Mononuclear, hexanuclear and polymeric indium(iii) pyrazolido complexes; structural characterization, dynamic solution studies and luminescent properties

Abstract

A new family of six mononuclear indium(III) complexes of formula mer-[InIIICl3(pz*H)3]—pz*H = pyrazole (pzH), or substituted pyrazoles: 4-Cl-pzH, 4-Br-pzH, 4-I-pzH, 4-Ph-pzH and 3,5-Me2-pzH—were synthesized by addition reactions of InCl3 and pz*H and crystallographically characterized. The fluxional behaviour of the complexes, probed by variable temperature 1H NMR spectroscopy in the 328 K to 173 K range, was attributed to (at least) four simultaneous processes: pyrazole N–H proton dissociation/association, cis/trans-pyrazole exchange, and N1/N2 tautomerization of the cis- and of the trans-pyrazoles. Three novel trianionic hexanuclear complexes of general formula (pipH)3[In6Cl63-OH0.5)2(μ-OH)6(μ-pz*)6]—pz* = pz, 4-Cl-pz and 4-Ph-pz—showing μ-hydroxo and μ-oxo bridges were synthesized from the corresponding mer-[InIIICl3(pz*H)3] and characterized by single crystal X-ray diffraction and 1H NMR. Under different solvent conditions, multicolour emitting polymeric complexes of general formula [In(μ-pz*)3]n—pz* = pz, 4-Cl-pz, 4-I-pz and 4-Ph-pz—were obtained also from mer-[InIIICl3(pz*H)3] after addition of a base. Luminescence and lifetime calculations were performed for all polymers formed.

Graphical abstract: Mononuclear, hexanuclear and polymeric indium(iii) pyrazolido complexes; structural characterization, dynamic solution studies and luminescent properties

Supplementary files

Article information

Article type
Paper
Submitted
15 jun 2022
Accepted
31 aug 2022
First published
01 sep 2022

Dalton Trans., 2022,51, 14277-14286

Mononuclear, hexanuclear and polymeric indium(III) pyrazolido complexes; structural characterization, dynamic solution studies and luminescent properties

S. Herrera, K. I. Rivero, A. Guzmán, J. Cedeño, J. Miksovska and R. G. Raptis, Dalton Trans., 2022, 51, 14277 DOI: 10.1039/D2DT01901A

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