1-Methyl-2-pyrrolidone: From exfoliating solvent to a paramagnetic ligand

A. A. Lemus-Santana, M. González, J. Rodríguez-Hernández, M. Knobel, E. Reguera

Research output: Contribution to journalArticle

13 Citations (Scopus)

Abstract

When 1-methyl-2-pyrrolidone molecule (1m2p) interacts with the T[Ni(CN)4] layer, its carbonyl π bond homolytically disrupts and forms a coordination bond at the axial positions for the metal T, and hybrid inorganic-organic solids of formula unit T(L)2[Ni(CN)4], with T = Mn, Co, Ni, are obtained. The formed solids crystallize with a monoclinic unit cell in the C2/m space group where the metal T is found with octahedral coordination to four N ends of CN groups from a given layer and to two oxygen atoms from the organic ligands, while the inner metal (Ni) preserves its square planar coordination. In the interlayer region, the organic molecules achieve unusual planarity and are stacked through dipole-dipole interactions in a head-to-tail configuration to form a chain of molecular pillars. From such interactions, 3D pillared hybrid solids result. Upon the charge donation to the metal by oxygen atom from 1m2p, the latter becomes an organic radical whose SOMO frontier orbital has a strong π character, associated with an essentially planar structure. The unpaired electron is delocalized between neighboring C and N atoms at the ligand ring plane, and it is featured by an outstanding broad absorption band in the near-IR region. For Ni, the metal of highest polarizing power within the considered series, the existence of π overlapping interaction between organic ligand molecules leads to ferromagnetic ordering at low temperature, with TC= 10.07 K. For Mn and Co, related to the lower metal electron-withdrawing ability, the materials maintain the weak antiferromagnetic character resulting from the interaction between T metals in the layer-T-NîC-Ni-CîN-T-chains. © 2013 American Chemical Society.
Original languageAmerican English
Pages (from-to)2400-2407
Number of pages2159
JournalJournal of Physical Chemistry A
DOIs
StatePublished - 21 Mar 2013

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Metals
Ligands
ligands
metals
Molecules
Atoms
molecules
oxygen atoms
interactions
Oxygen
dipoles
organic solids
Electrons
planar structures
2-pyrrolidone
Absorption spectra
interlayers
electrons
absorption spectra
orbitals

Cite this

@article{bd6606c17fe0444293783b925bc71356,
title = "1-Methyl-2-pyrrolidone: From exfoliating solvent to a paramagnetic ligand",
abstract = "When 1-methyl-2-pyrrolidone molecule (1m2p) interacts with the T[Ni(CN)4] layer, its carbonyl π bond homolytically disrupts and forms a coordination bond at the axial positions for the metal T, and hybrid inorganic-organic solids of formula unit T(L)2[Ni(CN)4], with T = Mn, Co, Ni, are obtained. The formed solids crystallize with a monoclinic unit cell in the C2/m space group where the metal T is found with octahedral coordination to four N ends of CN groups from a given layer and to two oxygen atoms from the organic ligands, while the inner metal (Ni) preserves its square planar coordination. In the interlayer region, the organic molecules achieve unusual planarity and are stacked through dipole-dipole interactions in a head-to-tail configuration to form a chain of molecular pillars. From such interactions, 3D pillared hybrid solids result. Upon the charge donation to the metal by oxygen atom from 1m2p, the latter becomes an organic radical whose SOMO frontier orbital has a strong π character, associated with an essentially planar structure. The unpaired electron is delocalized between neighboring C and N atoms at the ligand ring plane, and it is featured by an outstanding broad absorption band in the near-IR region. For Ni, the metal of highest polarizing power within the considered series, the existence of π overlapping interaction between organic ligand molecules leads to ferromagnetic ordering at low temperature, with TC= 10.07 K. For Mn and Co, related to the lower metal electron-withdrawing ability, the materials maintain the weak antiferromagnetic character resulting from the interaction between T metals in the layer-T-N{\^i}C-Ni-C{\^i}N-T-chains. {\circledC} 2013 American Chemical Society.",
author = "Lemus-Santana, {A. A.} and M. Gonz{\'a}lez and J. Rodr{\'i}guez-Hern{\'a}ndez and M. Knobel and E. Reguera",
year = "2013",
month = "3",
day = "21",
doi = "10.1021/jp4007813",
language = "American English",
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1-Methyl-2-pyrrolidone: From exfoliating solvent to a paramagnetic ligand. / Lemus-Santana, A. A.; González, M.; Rodríguez-Hernández, J.; Knobel, M.; Reguera, E.

In: Journal of Physical Chemistry A, 21.03.2013, p. 2400-2407.

Research output: Contribution to journalArticle

TY - JOUR

T1 - 1-Methyl-2-pyrrolidone: From exfoliating solvent to a paramagnetic ligand

AU - Lemus-Santana, A. A.

AU - González, M.

AU - Rodríguez-Hernández, J.

AU - Knobel, M.

AU - Reguera, E.

PY - 2013/3/21

Y1 - 2013/3/21

N2 - When 1-methyl-2-pyrrolidone molecule (1m2p) interacts with the T[Ni(CN)4] layer, its carbonyl π bond homolytically disrupts and forms a coordination bond at the axial positions for the metal T, and hybrid inorganic-organic solids of formula unit T(L)2[Ni(CN)4], with T = Mn, Co, Ni, are obtained. The formed solids crystallize with a monoclinic unit cell in the C2/m space group where the metal T is found with octahedral coordination to four N ends of CN groups from a given layer and to two oxygen atoms from the organic ligands, while the inner metal (Ni) preserves its square planar coordination. In the interlayer region, the organic molecules achieve unusual planarity and are stacked through dipole-dipole interactions in a head-to-tail configuration to form a chain of molecular pillars. From such interactions, 3D pillared hybrid solids result. Upon the charge donation to the metal by oxygen atom from 1m2p, the latter becomes an organic radical whose SOMO frontier orbital has a strong π character, associated with an essentially planar structure. The unpaired electron is delocalized between neighboring C and N atoms at the ligand ring plane, and it is featured by an outstanding broad absorption band in the near-IR region. For Ni, the metal of highest polarizing power within the considered series, the existence of π overlapping interaction between organic ligand molecules leads to ferromagnetic ordering at low temperature, with TC= 10.07 K. For Mn and Co, related to the lower metal electron-withdrawing ability, the materials maintain the weak antiferromagnetic character resulting from the interaction between T metals in the layer-T-NîC-Ni-CîN-T-chains. © 2013 American Chemical Society.

AB - When 1-methyl-2-pyrrolidone molecule (1m2p) interacts with the T[Ni(CN)4] layer, its carbonyl π bond homolytically disrupts and forms a coordination bond at the axial positions for the metal T, and hybrid inorganic-organic solids of formula unit T(L)2[Ni(CN)4], with T = Mn, Co, Ni, are obtained. The formed solids crystallize with a monoclinic unit cell in the C2/m space group where the metal T is found with octahedral coordination to four N ends of CN groups from a given layer and to two oxygen atoms from the organic ligands, while the inner metal (Ni) preserves its square planar coordination. In the interlayer region, the organic molecules achieve unusual planarity and are stacked through dipole-dipole interactions in a head-to-tail configuration to form a chain of molecular pillars. From such interactions, 3D pillared hybrid solids result. Upon the charge donation to the metal by oxygen atom from 1m2p, the latter becomes an organic radical whose SOMO frontier orbital has a strong π character, associated with an essentially planar structure. The unpaired electron is delocalized between neighboring C and N atoms at the ligand ring plane, and it is featured by an outstanding broad absorption band in the near-IR region. For Ni, the metal of highest polarizing power within the considered series, the existence of π overlapping interaction between organic ligand molecules leads to ferromagnetic ordering at low temperature, with TC= 10.07 K. For Mn and Co, related to the lower metal electron-withdrawing ability, the materials maintain the weak antiferromagnetic character resulting from the interaction between T metals in the layer-T-NîC-Ni-CîN-T-chains. © 2013 American Chemical Society.

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