Oxidative addition of halogens and pseudohalogens to dihalo(1,10-phenanthroline)platinum(II)

Hodges, Keith D.; Rund, John V.

doi:10.1021/ic50145a015

Cited by 77 publications

(46 citation statements)

References 2 publications

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“…Anhydrous CH 2 Cl 2 , diisopropylamine, and triethylamine were freshly distilled over CaH 2 . All of the other reagents from commercial sources were 36 Pt-(dppp)Cl 2 , 37 and Pt(dbbpy)(CtC-Ph) 2 (2) 2-4 were synthesized according to literature procedures and yielded satisfactory mass and 1 H NMR spectra.…”

Section: Methodsmentioning

confidence: 99%

Luminescent Charge-Transfer Platinum(II) Metallacycle

et al. 2007

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The photophysical and electrochemical properties of a platinum(II) diimine complex bearing the bidentate diacetylide ligand tolan-2,2'-diacetylide (tda), Pt(dbbpy)(tda) [dbbpy = 4,4'-di-tert-butyl-2,2'-bipyridine] (1), are compared with two reference compounds, Pt(dbbpy)(C[triple bond]CPh)(2) (2) and Pt(dppp)tda [dppp = 1,3-bis(diphenylphosphino)propane] (3), respectively. The X-ray crystal structure of 1 is reported, which illustrates the nearly perfect square planarity exhibited by this metallacycle. Chromophore 2 possesses low-lying charge-transfer excited states analogous to 1, whereas structure 3 lacks such excited states but features a low-lying platinum-perturbed tda intraligand triplet manifold. In CH(2)Cl(2), 1 exhibits a broad emission centered at 562 nm at ambient temperature, similar to 2, but with a higher photoluminescence quantum yield and longer excited-state lifetime. In both instances, the photoluminescence is consistent with triplet-charge-transfer excited-state parentage. The rigidity imposed by the cyclic diacetylide ligand in 1 leads to a reduction in nonradiative decay, which enhances its room-temperature photophysical properties. By comparison, 3 radiates highly structured tda-localized triplet-state phosphorescence at room temperature. The 77 K emission spectrum of 1 in 4:1 EtOH/MeOH becomes structured and is quantitatively similar to that measured for 3 under the same conditions. Because the 77 K spectra are nearly identical, the emissions are assigned as (3)tda in nature, implying that the charge-transfer states are raised in energy, relative to the (3)tda levels in 1 in the low-temperature glass. Nanosecond transient absorption spectrometry and ultrafast difference spectra were determined for 1-3 in CH(2)Cl(2) and DMF at ambient temperature. In 1 and 2, the major absorption transients are consistent with the one-electron reduced complexes, corroborated by reductive spectroelectrochemical measurements performed at room temperature. As 3 does not possess any charge-transfer character, excitation into the pipi* transitions of the tda ligand generated transient absorptions in the relaxed excited state assigned to the ligand-localized triplet state. In all three cases, the excited-state lifetimes measured by transient absorption are similar to those measured by time-resolved photoluminescence, suggesting that the same excited states giving rise to the photoluminescence are responsible for the absorption transients. ESR spectroscopy of the anions 1- and 2- and reductive spectroelectrochemistry of 1 and 2 revealed a LUMO based largely on the pi* orbital of the dbbpy ligand. Time-dependent density functional theory calculations performed on 1-3 both in vacuum and in a CH(2)Cl(2) continuum revealed the molecular orbitals, energies, dipole moments, and oscillator strengths for the various electronic transitions in these molecules. A DeltaSCF-method-derived shift applied to the calculated transition energies in the solvent continuum yielded good agreement between theory and experiment for each mo...

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Section: Methodsmentioning

confidence: 99%

Luminescent Charge-Transfer Platinum(II) Metallacycle

et al. 2007

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“…Treatment of [PtCl 2 (tBu 2 bpy)] [10] with two molar equivalents of 4-ethynylbenzo-15-crown-5 (L) [11] in the presence of copper() iodide and diisopropylamine afforded 1. The molecular structure of 1 (Figure 1) shows that the Pt II core is cis-coordinated by two 4-ethynylbenzo-15-crown-5 moieties and the tBu 2 bpy ligand.…”

Section: Resultsmentioning

confidence: 99%

“…All other solvents were of analytical grade and purified according to conventional methods. [16] 4,4Ј-Di-tert-butyl-2,2Ј-bipyridine, [17] [PtCl 2 (tBu 2 bpy)], [10] 4-ethynylbenzo-15-crown-5, [11] 6-phenyl-2,2Ј-bipyridine, [18] and [PtCl(C ∧ N ∧ N)] [12] were prepared by published methods. Fast atom bombardment (FAB) and electrospray mass spectra were obtained on a Finnigan MAT 95 (3-nitrobenzyl alcohol matrix) and LCQ quadrupole ion trap mass spectrometers, respectively.…”

Section: Methodsmentioning

confidence: 99%

A Diiminoplatinum(II) Complex of 4‐Ethynylbenzo‐15‐crown‐5 as a Luminescent Sensor for Divalent Metal Ions

Siu

Lai

et al. 2003

Eur J Inorg Chem

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The binding of a diiminoplatinum(II) complex of 4‐ethynylbenzo‐15‐crown‐5 to divalent metal ions such as Mg2+ or Zn2+ is accompanied by substantial enhancement of emission intensity (1035‐ and 870‐fold increase, respectively, with 40 equivalents of metal salt) at λmax ≈︁ 555 nm; H+, Cd2+ and alkali‐metal ions cause minor enhancement of the photoluminescence (⩽ 10‐fold) under similar conditions. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)

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“…Compound (1) and its Pt(II) products were synthesized and purified according to published procedures, [12] and [14], respectively, with slight modifications Scheme 1.…”

Section: Experimental Methodsmentioning

confidence: 99%

Synthesis and Structural Features of [4,4′-Diisopropoxyester-2,2′-bipyridine], [Dichloro(4,4′-diisopropoxyester-2,2′-bi-pyridine)-platinum(ii)] and Its Dichloromethane Solvated Pseudo-Polymorph: Versatile Supramolecular Interactions

et al. 2015

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The organic ligand 4,4 0 -diisopropoxyester-2,2 0 -bipyridine, C 18 H 20 N 2 O 4 (1), crystallizes in the triclinic crystal system P-1 and the molecule occupies a special position in the unit cell. In the crystal, molecules form stacks with partial overlapping of the pyridine rings. The Pt(II) dichloro complex of 1 crystallizes from a mixture of ethanol/hexane and from dichloromethane to form orange and yellow crystals, respectively. The orange non-solvated crystals of the (bipyridine)(dichloro)platinum(II) complex C 18 H 20 N 2 O 4 PtCl 2 (2) crystallize in the triclinic crystal system P-1 as well with two independent molecules in the unit cell. In the crystal packing, molecules form two types of dimers with Pt1ÁÁÁPt1A and Pt2ÁÁÁPt2A distances of 3.478 and 5.186 Å , respectively. The yellow crystals, as a solvated pseudo-polymorph C 18 H 20 N 2 O 4 PtCl 2 Á1.5 CH 2 Cl 2 (3) also crystallize in the triclinic crystal system P-1 with two independent molecules in the unit cell. In the crystal packing, molecules form Pt2ÁÁÁPt1ÁÁÁPt1AÁÁÁPt2A intermolecular contacts with alternating distances 3.501 and 3.431 Å , respectively, forming infinite chains. Graphical Abstract The dichloro(bipyridine)platinum complex, dichloro(4,4 0 -diisopropoxyester-2,2 0 -bipyridine)-platinum(II), forms single crystals as a stable non-solvated form and a solvated polymorph with dramatically different supramolecular structure and short contacts.Keywords X-ray diffraction Á [4,4 0 -diisopropoxyester-2, 2 0 -bi-pyridine] Á [dichloro(4, 4 0 -diisopropoxyester-2, 2 0 -bipyridine)-platinum(II)] Á Supramolecular interactions Á Pseudo-polymorphism

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Oxidative addition of halogens and pseudohalogens to dihalo(1,10-phenanthroline)platinum(II)

Cited by 77 publications

References 2 publications

Luminescent Charge-Transfer Platinum(II) Metallacycle

Luminescent Charge-Transfer Platinum(II) Metallacycle

A Diiminoplatinum(II) Complex of 4‐Ethynylbenzo‐15‐crown‐5 as a Luminescent Sensor for Divalent Metal Ions

Synthesis and Structural Features of [4,4′-Diisopropoxyester-2,2′-bipyridine], [Dichloro(4,4′-diisopropoxyester-2,2′-bi-pyridine)-platinum(ii)] and Its Dichloromethane Solvated Pseudo-Polymorph: Versatile Supramolecular Interactions

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