Heteroleptic binuclear palladium(ii) and platinum(ii) complexes containing 1,2-bis(diphenylphosphino)acetylene and 1,2-benzenedithiolates: Syntheses, crystal structures, electrochemistry and photoluminescence properties

Kyong Soon Shin, Kyung In Son, Jae Il Kim, Chang Seop Hong, Myungkoo Suh, Dong Youn Noh

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Abstract

A series of heteroleptic binuclear Pd(ii) and Pt(ii) complexes, [M(bdts)]2(μ-dppa)2 (M = Pd (3) and Pt (4); dppa = 1,2-bis(diphenylphosphino)acetylene = Ph2PC≡CPPh2; bdts = 1,2-benzenedithiolate (bdt: a), 3,4-toluenedithiolate (tdt: b) and 1,4-dichloro-2,3-benzenedithiolate (Cl2bdt: c), containing two square-planar MP2S2 cores were prepared using (MCl2)2(μ-dppa)2 (M = Pd (1) and Pt (2)) and the corresponding 1,2-benzenedithiols, and characterized by spectroscopic methods including FT-IR, Raman, UV-vis, MALDI-TOF-MS, 31P(1H) and/or 195Pt(1H) NMR spectroscopy. X-Ray crystal structure analyses for complexes 3 and 4 revealed that C1C2C4C3 is twisted in two ways with a torsion angle of 21.6–30.7° for 3a, 3b, 4a and 4b and about 42° for 3c and 4c, and that their crystals are racemic mixtures. Due to the more electronegative chloride atoms in the ligand, complexes 3c and 4c show higher ν(M–S) vibrational frequencies in their Raman spectra, smaller spin–spin coupling constants (JPt–P) in their 195Pt(31P) NMR spectra and higher anodic potentials (Epa) in their cyclic voltammograms than complexes 3a, 3b, 4a and 4b. Moreover, only complex 4c containing the chlorinated ligand and Pt(ii) ion exhibits luminescence (λob = 610 nm andλex = 440 nm) in the solid state at 298 K. This emissive transition can be assigned as the d–Π*dithiolate metal-to-ligand charge transfer (MLCT) and the feasibility of this spin-forbidden transition is ascribed to the effective spin–orbit coupling of ligand c containing heavy chloride atoms and the large spin–orbit coupling in Pt(ii).

Original languageEnglish
Pages (from-to)1767-1775
Number of pages9
JournalJournal of the Chemical Society. Dalton Transactions
Issue number10
DOIs
Publication statusPublished - 2009 Feb 24

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Acetylene
Palladium
Electrochemistry
Platinum
Photoluminescence
Crystal structure
Ligands
Chlorides
Atoms
Vibrational spectra
Torsional stress
Nuclear magnetic resonance spectroscopy
Charge transfer
Raman scattering
Luminescence
Metals
Nuclear magnetic resonance
Ions
X rays
Crystals

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

@article{f3395e22734a4e8595ae60da3b830a1d,
title = "Heteroleptic binuclear palladium(ii) and platinum(ii) complexes containing 1,2-bis(diphenylphosphino)acetylene and 1,2-benzenedithiolates: Syntheses, crystal structures, electrochemistry and photoluminescence properties",
abstract = "A series of heteroleptic binuclear Pd(ii) and Pt(ii) complexes, [M(bdts)]2(μ-dppa)2 (M = Pd (3) and Pt (4); dppa = 1,2-bis(diphenylphosphino)acetylene = Ph2PC≡CPPh2; bdts = 1,2-benzenedithiolate (bdt: a), 3,4-toluenedithiolate (tdt: b) and 1,4-dichloro-2,3-benzenedithiolate (Cl2bdt: c), containing two square-planar MP2S2 cores were prepared using (MCl2)2(μ-dppa)2 (M = Pd (1) and Pt (2)) and the corresponding 1,2-benzenedithiols, and characterized by spectroscopic methods including FT-IR, Raman, UV-vis, MALDI-TOF-MS, 31P(1H) and/or 195Pt(1H) NMR spectroscopy. X-Ray crystal structure analyses for complexes 3 and 4 revealed that C1C2C4C3 is twisted in two ways with a torsion angle of 21.6–30.7° for 3a, 3b, 4a and 4b and about 42° for 3c and 4c, and that their crystals are racemic mixtures. Due to the more electronegative chloride atoms in the ligand, complexes 3c and 4c show higher ν(M–S) vibrational frequencies in their Raman spectra, smaller spin–spin coupling constants (JPt–P) in their 195Pt(31P) NMR spectra and higher anodic potentials (Epa) in their cyclic voltammograms than complexes 3a, 3b, 4a and 4b. Moreover, only complex 4c containing the chlorinated ligand and Pt(ii) ion exhibits luminescence (λob = 610 nm andλex = 440 nm) in the solid state at 298 K. This emissive transition can be assigned as the d–Π*dithiolate metal-to-ligand charge transfer (MLCT) and the feasibility of this spin-forbidden transition is ascribed to the effective spin–orbit coupling of ligand c containing heavy chloride atoms and the large spin–orbit coupling in Pt(ii).",
author = "Shin, {Kyong Soon} and Son, {Kyung In} and Kim, {Jae Il} and Hong, {Chang Seop} and Myungkoo Suh and Noh, {Dong Youn}",
year = "2009",
month = "2",
day = "24",
doi = "10.1039/b815013c",
language = "English",
pages = "1767--1775",
journal = "Dalton Transactions",
issn = "1472-7773",
publisher = "Royal Society of Chemistry",
number = "10",

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TY - JOUR

T1 - Heteroleptic binuclear palladium(ii) and platinum(ii) complexes containing 1,2-bis(diphenylphosphino)acetylene and 1,2-benzenedithiolates

T2 - Syntheses, crystal structures, electrochemistry and photoluminescence properties

AU - Shin, Kyong Soon

AU - Son, Kyung In

AU - Kim, Jae Il

AU - Hong, Chang Seop

AU - Suh, Myungkoo

AU - Noh, Dong Youn

PY - 2009/2/24

Y1 - 2009/2/24

N2 - A series of heteroleptic binuclear Pd(ii) and Pt(ii) complexes, [M(bdts)]2(μ-dppa)2 (M = Pd (3) and Pt (4); dppa = 1,2-bis(diphenylphosphino)acetylene = Ph2PC≡CPPh2; bdts = 1,2-benzenedithiolate (bdt: a), 3,4-toluenedithiolate (tdt: b) and 1,4-dichloro-2,3-benzenedithiolate (Cl2bdt: c), containing two square-planar MP2S2 cores were prepared using (MCl2)2(μ-dppa)2 (M = Pd (1) and Pt (2)) and the corresponding 1,2-benzenedithiols, and characterized by spectroscopic methods including FT-IR, Raman, UV-vis, MALDI-TOF-MS, 31P(1H) and/or 195Pt(1H) NMR spectroscopy. X-Ray crystal structure analyses for complexes 3 and 4 revealed that C1C2C4C3 is twisted in two ways with a torsion angle of 21.6–30.7° for 3a, 3b, 4a and 4b and about 42° for 3c and 4c, and that their crystals are racemic mixtures. Due to the more electronegative chloride atoms in the ligand, complexes 3c and 4c show higher ν(M–S) vibrational frequencies in their Raman spectra, smaller spin–spin coupling constants (JPt–P) in their 195Pt(31P) NMR spectra and higher anodic potentials (Epa) in their cyclic voltammograms than complexes 3a, 3b, 4a and 4b. Moreover, only complex 4c containing the chlorinated ligand and Pt(ii) ion exhibits luminescence (λob = 610 nm andλex = 440 nm) in the solid state at 298 K. This emissive transition can be assigned as the d–Π*dithiolate metal-to-ligand charge transfer (MLCT) and the feasibility of this spin-forbidden transition is ascribed to the effective spin–orbit coupling of ligand c containing heavy chloride atoms and the large spin–orbit coupling in Pt(ii).

AB - A series of heteroleptic binuclear Pd(ii) and Pt(ii) complexes, [M(bdts)]2(μ-dppa)2 (M = Pd (3) and Pt (4); dppa = 1,2-bis(diphenylphosphino)acetylene = Ph2PC≡CPPh2; bdts = 1,2-benzenedithiolate (bdt: a), 3,4-toluenedithiolate (tdt: b) and 1,4-dichloro-2,3-benzenedithiolate (Cl2bdt: c), containing two square-planar MP2S2 cores were prepared using (MCl2)2(μ-dppa)2 (M = Pd (1) and Pt (2)) and the corresponding 1,2-benzenedithiols, and characterized by spectroscopic methods including FT-IR, Raman, UV-vis, MALDI-TOF-MS, 31P(1H) and/or 195Pt(1H) NMR spectroscopy. X-Ray crystal structure analyses for complexes 3 and 4 revealed that C1C2C4C3 is twisted in two ways with a torsion angle of 21.6–30.7° for 3a, 3b, 4a and 4b and about 42° for 3c and 4c, and that their crystals are racemic mixtures. Due to the more electronegative chloride atoms in the ligand, complexes 3c and 4c show higher ν(M–S) vibrational frequencies in their Raman spectra, smaller spin–spin coupling constants (JPt–P) in their 195Pt(31P) NMR spectra and higher anodic potentials (Epa) in their cyclic voltammograms than complexes 3a, 3b, 4a and 4b. Moreover, only complex 4c containing the chlorinated ligand and Pt(ii) ion exhibits luminescence (λob = 610 nm andλex = 440 nm) in the solid state at 298 K. This emissive transition can be assigned as the d–Π*dithiolate metal-to-ligand charge transfer (MLCT) and the feasibility of this spin-forbidden transition is ascribed to the effective spin–orbit coupling of ligand c containing heavy chloride atoms and the large spin–orbit coupling in Pt(ii).

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