Heteropolynuclear Pt(II)–M(I) clusters with a C∧N∧C biscyclometalated ligand

Sara Fuertes, Christopher H. Woodall, Paul R. Raithby, Violeta Sicilia

Research output: Contribution to journalArticle

  • 21 Citations

Abstract

The mononuclear complex [(EtO2C-CNC)Pt(dmpyz)] (1) (dmpyz = 2,5-dimethylpyrazine) has been synthesized by reaction of [(EtO2C-CNC)Pt(dmso)] (A) with dmpyz in a 1:1 molar ratio in dichloromethane. Complex 1 is the precursor for preparing the homodinuclear complex [{(EtO2C-CNC)Pt}2(μ-dmpyz)] (2) and the heterotrinuclear clusters [{(EtO2C-CNC)Pt(dmpyz)}2M]X (M = Cu, X = PF6 (3); M = Ag, X = BF4 (4)). Compounds 1, 2, and 4 were studied by X-ray diffraction methods. In the crystal packing of 1 and 2, the molecules display short intermolecular π···π contacts, which control the solid-state emissive behavior. X-ray study on 4 shows two [Pt2Ag] sandwich-type clusters in the asymmetric unit, both with the two square-planar “(R-CNC)Pt(dmpyz)” moieties stabilized by two Pt → Ag donor–acceptor bonds as well as by η1- and η2-Ag–C interactions. Intramolecular π–π contacts were found between the pyridine rings of the CNC ligands within the same Pt2Ag cluster. 1H and 195Pt NMR studies confirm that the Pt2M cluster is also retained in solution at room temperature. 195Pt NMR spectra of 3 and 4 show signals shifted significantly downfield when comparing with that for the monomer (1), which is attributed to the presence of Pt–M dative bonds. At lower temperatures (T = 193 K), the copper derivative definitely falls apart, whereas the silver one still holds up unbroken. In the solid state at 77 K, compounds 1–4 give red emissions arising from 3ππ excited states due to the intra- or intermolecular π–π contacts observed in the crystal structures. As expected, in glassy solutions (77 K), compound 3 displays analogous emissions to those from the starting material (1). Complexes 1 and 2 show structured emission bands that are particularly sensitive to the λex (HE and LE). In contrast, 4 displays an unstructured emission at 680 nm with a shoulder at 556 nm; both are not dependent on the λex. DFT and TDDFT computational studies have been performed on 1 and 2, which support the conclusions drawn from the photophysical studies.
LanguageEnglish
Pages4228-4240
JournalOrganometallics
Volume31
Issue number11
DOIs
StatusPublished - 11 Jun 2012

Fingerprint

Nuclear magnetic resonance
Ligands
ligands
Methylene Chloride
Silver
Excited states
Discrete Fourier transforms
Copper
Monomers
Crystal structure
Display devices
Derivatives
solid state
X ray diffraction
X rays
Temperature
nuclear magnetic resonance
Crystals
Molecules
shoulders

Cite this

Heteropolynuclear Pt(II)–M(I) clusters with a C∧N∧C biscyclometalated ligand. / Fuertes, Sara; Woodall, Christopher H.; Raithby, Paul R.; Sicilia, Violeta.

In: Organometallics, Vol. 31, No. 11, 11.06.2012, p. 4228-4240.

Research output: Contribution to journalArticle

Fuertes, S, Woodall, CH, Raithby, PR & Sicilia, V 2012, 'Heteropolynuclear Pt(II)–M(I) clusters with a C∧N∧C biscyclometalated ligand' Organometallics, vol. 31, no. 11, pp. 4228-4240. DOI: 10.1021/om300170j
Fuertes S, Woodall CH, Raithby PR, Sicilia V. Heteropolynuclear Pt(II)–M(I) clusters with a C∧N∧C biscyclometalated ligand. Organometallics. 2012 Jun 11;31(11):4228-4240. Available from, DOI: 10.1021/om300170j
Fuertes, Sara ; Woodall, Christopher H. ; Raithby, Paul R. ; Sicilia, Violeta. / Heteropolynuclear Pt(II)–M(I) clusters with a C∧N∧C biscyclometalated ligand. In: Organometallics. 2012 ; Vol. 31, No. 11. pp. 4228-4240
@article{294fd21f59a7481dbfd8043793308bb1,
title = "Heteropolynuclear Pt(II)–M(I) clusters with a C∧N∧C biscyclometalated ligand",
abstract = "The mononuclear complex [(EtO2C-CNC)Pt(dmpyz)] (1) (dmpyz = 2,5-dimethylpyrazine) has been synthesized by reaction of [(EtO2C-CNC)Pt(dmso)] (A) with dmpyz in a 1:1 molar ratio in dichloromethane. Complex 1 is the precursor for preparing the homodinuclear complex [{(EtO2C-CNC)Pt}2(μ-dmpyz)] (2) and the heterotrinuclear clusters [{(EtO2C-CNC)Pt(dmpyz)}2M]X (M = Cu, X = PF6 (3); M = Ag, X = BF4 (4)). Compounds 1, 2, and 4 were studied by X-ray diffraction methods. In the crystal packing of 1 and 2, the molecules display short intermolecular π···π contacts, which control the solid-state emissive behavior. X-ray study on 4 shows two [Pt2Ag] sandwich-type clusters in the asymmetric unit, both with the two square-planar “(R-CNC)Pt(dmpyz)” moieties stabilized by two Pt → Ag donor–acceptor bonds as well as by η1- and η2-Ag–C interactions. Intramolecular π–π contacts were found between the pyridine rings of the CNC ligands within the same Pt2Ag cluster. 1H and 195Pt NMR studies confirm that the Pt2M cluster is also retained in solution at room temperature. 195Pt NMR spectra of 3 and 4 show signals shifted significantly downfield when comparing with that for the monomer (1), which is attributed to the presence of Pt–M dative bonds. At lower temperatures (T = 193 K), the copper derivative definitely falls apart, whereas the silver one still holds up unbroken. In the solid state at 77 K, compounds 1–4 give red emissions arising from 3ππ excited states due to the intra- or intermolecular π–π contacts observed in the crystal structures. As expected, in glassy solutions (77 K), compound 3 displays analogous emissions to those from the starting material (1). Complexes 1 and 2 show structured emission bands that are particularly sensitive to the λex (HE and LE). In contrast, 4 displays an unstructured emission at 680 nm with a shoulder at 556 nm; both are not dependent on the λex. DFT and TDDFT computational studies have been performed on 1 and 2, which support the conclusions drawn from the photophysical studies.",
author = "Sara Fuertes and Woodall, {Christopher H.} and Raithby, {Paul R.} and Violeta Sicilia",
year = "2012",
month = "6",
day = "11",
doi = "10.1021/om300170j",
language = "English",
volume = "31",
pages = "4228--4240",
journal = "Organometallics",
issn = "0276-7333",
publisher = "American Chemical Society",
number = "11",

}

TY - JOUR

T1 - Heteropolynuclear Pt(II)–M(I) clusters with a C∧N∧C biscyclometalated ligand

AU - Fuertes,Sara

AU - Woodall,Christopher H.

AU - Raithby,Paul R.

AU - Sicilia,Violeta

PY - 2012/6/11

Y1 - 2012/6/11

N2 - The mononuclear complex [(EtO2C-CNC)Pt(dmpyz)] (1) (dmpyz = 2,5-dimethylpyrazine) has been synthesized by reaction of [(EtO2C-CNC)Pt(dmso)] (A) with dmpyz in a 1:1 molar ratio in dichloromethane. Complex 1 is the precursor for preparing the homodinuclear complex [{(EtO2C-CNC)Pt}2(μ-dmpyz)] (2) and the heterotrinuclear clusters [{(EtO2C-CNC)Pt(dmpyz)}2M]X (M = Cu, X = PF6 (3); M = Ag, X = BF4 (4)). Compounds 1, 2, and 4 were studied by X-ray diffraction methods. In the crystal packing of 1 and 2, the molecules display short intermolecular π···π contacts, which control the solid-state emissive behavior. X-ray study on 4 shows two [Pt2Ag] sandwich-type clusters in the asymmetric unit, both with the two square-planar “(R-CNC)Pt(dmpyz)” moieties stabilized by two Pt → Ag donor–acceptor bonds as well as by η1- and η2-Ag–C interactions. Intramolecular π–π contacts were found between the pyridine rings of the CNC ligands within the same Pt2Ag cluster. 1H and 195Pt NMR studies confirm that the Pt2M cluster is also retained in solution at room temperature. 195Pt NMR spectra of 3 and 4 show signals shifted significantly downfield when comparing with that for the monomer (1), which is attributed to the presence of Pt–M dative bonds. At lower temperatures (T = 193 K), the copper derivative definitely falls apart, whereas the silver one still holds up unbroken. In the solid state at 77 K, compounds 1–4 give red emissions arising from 3ππ excited states due to the intra- or intermolecular π–π contacts observed in the crystal structures. As expected, in glassy solutions (77 K), compound 3 displays analogous emissions to those from the starting material (1). Complexes 1 and 2 show structured emission bands that are particularly sensitive to the λex (HE and LE). In contrast, 4 displays an unstructured emission at 680 nm with a shoulder at 556 nm; both are not dependent on the λex. DFT and TDDFT computational studies have been performed on 1 and 2, which support the conclusions drawn from the photophysical studies.

AB - The mononuclear complex [(EtO2C-CNC)Pt(dmpyz)] (1) (dmpyz = 2,5-dimethylpyrazine) has been synthesized by reaction of [(EtO2C-CNC)Pt(dmso)] (A) with dmpyz in a 1:1 molar ratio in dichloromethane. Complex 1 is the precursor for preparing the homodinuclear complex [{(EtO2C-CNC)Pt}2(μ-dmpyz)] (2) and the heterotrinuclear clusters [{(EtO2C-CNC)Pt(dmpyz)}2M]X (M = Cu, X = PF6 (3); M = Ag, X = BF4 (4)). Compounds 1, 2, and 4 were studied by X-ray diffraction methods. In the crystal packing of 1 and 2, the molecules display short intermolecular π···π contacts, which control the solid-state emissive behavior. X-ray study on 4 shows two [Pt2Ag] sandwich-type clusters in the asymmetric unit, both with the two square-planar “(R-CNC)Pt(dmpyz)” moieties stabilized by two Pt → Ag donor–acceptor bonds as well as by η1- and η2-Ag–C interactions. Intramolecular π–π contacts were found between the pyridine rings of the CNC ligands within the same Pt2Ag cluster. 1H and 195Pt NMR studies confirm that the Pt2M cluster is also retained in solution at room temperature. 195Pt NMR spectra of 3 and 4 show signals shifted significantly downfield when comparing with that for the monomer (1), which is attributed to the presence of Pt–M dative bonds. At lower temperatures (T = 193 K), the copper derivative definitely falls apart, whereas the silver one still holds up unbroken. In the solid state at 77 K, compounds 1–4 give red emissions arising from 3ππ excited states due to the intra- or intermolecular π–π contacts observed in the crystal structures. As expected, in glassy solutions (77 K), compound 3 displays analogous emissions to those from the starting material (1). Complexes 1 and 2 show structured emission bands that are particularly sensitive to the λex (HE and LE). In contrast, 4 displays an unstructured emission at 680 nm with a shoulder at 556 nm; both are not dependent on the λex. DFT and TDDFT computational studies have been performed on 1 and 2, which support the conclusions drawn from the photophysical studies.

UR - http://www.scopus.com/inward/record.url?scp=84862152723&partnerID=8YFLogxK

UR - http://dx.doi.org/10.1021/om300170j

U2 - 10.1021/om300170j

DO - 10.1021/om300170j

M3 - Article

VL - 31

SP - 4228

EP - 4240

JO - Organometallics

T2 - Organometallics

JF - Organometallics

SN - 0276-7333

IS - 11

ER -