NMR thermosensing properties on binuclear triple-decker complexes of terbium(III) and dysprosium(III) with 15-crown-5-phthalocyanine

Babailov, Sergey P.; Polovkova, Marina A.; Kirakosyan, G. A.; Martynov, Alexander G.; Zapolotsky, Eugeny N.; Gorbunova, Yulia G.

doi:10.1016/j.sna.2021.112933

Cited by 19 publications

(9 citation statements)

References 52 publications

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“…NMR spectra of synthesized complexes are provided in Supplementary Information (Figures S2, S4, S6 and S8) . Analytical characteristics of the synthesized complexes were in agreement with the previously reported data [ 63 , 64 ].…”

Section: Methodssupporting

confidence: 90%

Redox-Triggered Switching of Conformational State in Triple-Decker Lanthanide Phthalocyaninates

et al. 2022

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Double- and triple-decker lanthanide phthalocyaninates exhibit unique physical-chemical properties, particularly single-molecule magnetism. Among other factors, the magnetic properties of these sandwiches depend on their conformational state, which is determined via the skew angle of the phthalocyanine ligands. Thus, in the present work we report the comprehensive conformational study of substituted terbium(III) and yttrium(III) trisphthalocyaninates in solution depending on the substituents at the periphery of molecules, redox-states and nature of solvents. Conjunction of UV-vis-NIR spectroscopy and quantum-chemical calculations within simplified time-dependent DFT in Tamm–Dancoff approximation provided the spectroscopic signatures of staggered and gauche conformations of trisphthalocyaninates. Altogether, it allowed us to demonstrate that the butoxy-substituted complex behaves as a molecular switcher with controllable conformational state, while the crown-substituted triple-decker complex maintains a staggered conformation regardless of external factors. The analysis of noncovalent interactions within the reduced density gradient approach allowed to shed light on the nature of factors stabilizing certain conformers.

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Section: Methodssupporting

confidence: 90%

Redox-Triggered Switching of Conformational State in Triple-Decker Lanthanide Phthalocyaninates

et al. 2022

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“…The phenomenon was also found to be general for most of bisphthalocyaninates, which are formed by lanthanides exhibiting di-and trivalent states -Sm, Eu, Er, Tm, and Yb. 62,63 Homonuclear trisphthalocyaninates of strongly paramagnetic lanthanides -Ln 2 [(15C5) 4 Pc] 3 , Ln = Tb, Dy, Ho, and Tm were studied by variable-temperature NMR showing the possibility of their application as thermosensors in the physiological temperature range (303-323 K) 64,65 due to the sensitivity of lanthanide-induced shifts to temperature. The Tb(III) complex was found to have the highest sensitivity of this shift among the reported paramagnetic complexes of 4f and d elements with polydentate ligands in organic media.…”

Section: Advances In the Synthesis Of Functionalized Multiple-decker ...mentioning

confidence: 99%

Rare-earth based tetrapyrrolic sandwiches: chemistry, materials and applications

et al. 2022

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“…Complexes of 3:2 stoichiometry—triple-decker sandwich type—were reported for a significant number of systems including various types of ligands and metal centers. This type of complexes are common in transition metal chemistry [ 36 ] and lanthanides [ 37 ]. Moreover, for barium, such sandwich complex was reported [ 38 ].…”

Section: Resultsmentioning

confidence: 99%

Novel Diazocrowns with Pyrrole Residue as Lead(II)Colorimetric Probes

et al. 2021

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Novel 18- and 23-membered diazomacrocycles were obtained with satisfactory yields by diazocoupling of aromatic diamines with pyrrole in reactions carried under high dilution conditions. X-ray structure of macrocycle bearing five carbon atoms linkage was determined and described. Compounds were characterized as chromogenic heavy metal ions receptors. Selective color and spectral response for lead(II) was found in acetonitrile and its mixture with water. Complexation properties of newly obtained macrocycles with a hydrocarbon chain were compared with the properties of their oligoether analogs. The influence of the introduction of hydrocarbon residue as a part of macrocycle on the lead(II) binding was discussed. Selective and sensitive colorimetric probe for lead(II) in aqueous acetonitrile with detection limit 56.1 μg/L was proposed.

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NMR thermosensing properties on binuclear triple-decker complexes of terbium(III) and dysprosium(III) with 15-crown-5-phthalocyanine

Cited by 19 publications

References 52 publications

Redox-Triggered Switching of Conformational State in Triple-Decker Lanthanide Phthalocyaninates

Redox-Triggered Switching of Conformational State in Triple-Decker Lanthanide Phthalocyaninates

Rare-earth based tetrapyrrolic sandwiches: chemistry, materials and applications

Novel Diazocrowns with Pyrrole Residue as Lead(II)Colorimetric Probes

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