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
Y1 - 2009
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 = Ph2PCCPPh2; 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 (MCl 2)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 and λex = 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 = Ph2PCCPPh2; 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 (MCl 2)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 and λex = 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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U2 - 10.1039/b815013c
DO - 10.1039/b815013c
M3 - Article
C2 - 19240910
AN - SCOPUS:61349118824
SN - 1477-9226
SP - 1767
EP - 1775
JO - Dalton Transactions
JF - Dalton Transactions
IS - 10
ER -