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At least 523 records · Page 29Linked to original sources
PubMed2005

Phosphorescent organogels via "metallophilic" interactions for reversible RGB-color switching.

A trinuclear Au(I) pyrazolate complex bearing long alkyl chains (1) in hexane self-assembles via a Au(I)-Au(I) metallophilic interaction, to form a red-luminescent organogel (lambda(em) = 640 nm, lambda(ext) = 284 nm). Scanning electron microscopy (SEM) and X-ray diffraction (XRD) analysis of an air-dried gel with 1 show the presence of heavily entangled fibers, each consisting of a rectangularly packed columnar assembly of 1. Doping of the organogel with a small amount of Ag(+) results in a blue luminescence (lambda(em) = 458 nm, lambda(ext) = 370 nm) without disruption of the gel, while removal of doped Ag(+) with cetyltrimethylammonium chloride results in complete recovery of the original red-luminescent gel. Upon heating, these organogels undergo gel-to-sol transition due to the destabilization of the metallophilic interactions, where the red luminescence of the nondoped system becomes hardly visible, while the blue luminescence of the Ag(+)-doped system turns green (lambda(em) = 501 nm, lambda(ext) = 370 nm). On cooling, these solutions undergo gelation and synchronously recover the original luminescences. The observed RGB (red-green-blue) luminescences are all long-lived (3-6 micros) and assigned to electronic transitions from triplet-excited states.

Journal Article↗
PubMed2005

Excited states of phosphorescent platinum(II) complexes containing N wedge C wedge N-coordinating tridentate ligands: spectroscopic investigations and time-dependent density functional theory calculations.

The absorption and emission spectra of the Pt(II) complexes containing N wedge C wedge N-coordinating tridentate ligands, platinum(II) 1,3-di(2-pyridyl)benzene chloride [Pt(dpb)Cl] and platinum(II) 3,5-di(2-pyridyl)toluene chloride [Pt(dpt)Cl], together with their corresponding free ligands, 1,3-di(2-pyridyl)benzene (dpbH) and 3,5-di(2-pyridyl)toluene (dptH), have been analyzed by density functional theory (DFT) for the ground state and time-dependent DFT (TDDFT) for the excited states. T(1)(A(1)) and S(1)(B(2)) of the complexes (in C(2)(v) symmetry) were assigned on the basis of the calculated excitation energies as well as comparison of the experimental spectroscopic properties and the calculated states' characteristics. The calculated excitation energies for T(1) and S(1) of the complexes as well as those for T(1) of the free ligands were in good agreement with their observed values within 600 cm(-1). The d-pi* characters of the excited states were evaluated from the change in electron densities between the ground and excited states by Mulliken population analysis; values of 25% for T(1) and 32% for S(1) were obtained for both complexes. The calculated values of d-pi* character were found to be consistent with the reported emission lifetimes as well as the observed emission energy shifts from the corresponding free ligands. Most spectroscopic properties of the complexes and the free ligands, which include solvatochromic shift, Stokes shifts, methyl substitution shifts, and emission spectra profiles, were well explained from the calculation results.

Journal Article↗
PubMed2005

Existence of intramolecular triplet excimer of bis(9-fluorenyl)methane: phosphorescence and delayed fluorescence spectroscopic and ab initio studies.

A concerted computational and experimental study has been undertaken to probe the conformational structure and excited-state dynamics of bis(9-fluorenyl)methane (BFM). We have observed that the relative intensity of the delayed excimer fluorescence of BFM is greatly enhanced in comparison with that of the normal fluorescence. This is presumably because the relative concentration of the triplet excimer is enhanced in comparison with the singlet excimer. B3LYP DFT/6-31G(d) calculations indicate that the sandwich conformer of BFM in the singlet ground state is unstable, whereas that in the triplet excited state has a bound state, being very slightly higher in internal and Gibbs free energies than that of the lowest state of the near-orthogonal conformer.

Journal Article↗
PubMed2007

Electronic structures and spectroscopic properties of mono- and binuclear d(8) complexes: a theoretical exploration on promising phosphorescent materials.

The structures of trans-[M(2)(CN)(4)(PH(2)CH(2)PH(2))(2)] (M = Pt (1), Pd (2), and Ni (3)), trans-[Pt(2)X(4)(PH(2)CH(2)PH(2))(2)] (X = Cl (4) and Br (5)), and trans-[M(CN)(2)(PH(3))(2)] (M = Pt (6), Pd (7), and Ni (8)) in the ground state were optimized using the MP2 method. Frequency calculations reveal that the weak metal-metal interaction is essentially attractive for 1, 2, 4, and 5 but not for 3. The TD-DFT calculations associated with the polarized continuum model (PCM) were performed to predict absorption spectra in CH(2)Cl(2) solution. Experimental spectra are well reproduced by our results. With respect to analogous mononuclear d(8) complexes (6-8), a large red shift of the absorption wavelength was calculated for the binuclear d(8) complexes (1-3). Relative to 1 with unsaturated CN- donors, introduction of saturated halogen donors into 4 and 5 changes their electronic structures, especially the HOMO and LUMO. The TD-DFT and subsequent unrestricted MP2 calculations predict that 1 produces the lowest-energy d --> p emission while 2-5 favor the d --> d emissions, agreeing with experimental observations.

Journal Article↗
PubMed2004

Tetradentate Schiff base platinum(II) complexes as new class of phosphorescent materials for high-efficiency and white-light electroluminescent devices.

The capabilities of readily prepared and sublimable Pt(II) Schiff base triplet emitters as OLED dopants have been examined; maximum luminous and power efficiencies and luminance of 31 cd A(-1), 14 lm W(-1), and 23,000 cd m(-2), respectively, and white EL (CIE: 0.33, 0.35) by simultaneous host/dopant emission, have been achieved.

Journal Article↗
PubMed2004

Self-aggregated phosphorescent platinum(II) polymeric material from modified poly(4-vinylpyridine).

A solvochromic material made from incorporation of photoluminescent Pt(II)([formula: see text]) moieties into commercially available homopolymer poly(4-vinylpyridine) exhibits different emission energies, due to different degrees of self-aggregation in various solvents and as thin film upon exposure to vapour of different volatile organic compounds (VOC); self-aggregation enables intra- and intermolecular interactions arising from pi-stacking of the Pt([formula: see text]) moieties, which is affected by medium polarity.

Luminescent Measurements↗