Luminescence Vapochromism of a Platinum(II) Complex for Detection of Low Molecular Weight Halohydrocarbon

Ni, Jun; Wu, Yu; Zhang, Xu; Li, Bin; Zhang, Li Yi; Chen, Zhong Ning

doi:10.1021/ic9011982

Cited by 82 publications

(35 citation statements)

References 69 publications

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“…The absorption bands < 330 nm are mainly ascribable to ligand-centered transitions. With reference to the relevant literature, [39] the low-energy broad bands centered at about 440 nm result mostly likely from both dp(Pt)!p*(Me 3 LLCT (ligand-to-ligand charge transfer) transitions as revealed from DFT studies (vide infra). The broad low-energy absorption bands in 2-4 are solvent-dependent, but insensitive to solution concentrations.…”

Section: Resultsmentioning

confidence: 99%

“…The staggered packing pattern with one planar platinum(II) moiety rotated at an angle relative to an adjacent one usually favors a conformation in close proximity to form short Pt···Pt distance (< 3.4 ) and substantial metallophilic Pt-Pt interactions. [39] The antiparallel pattern, however, always induces adjacent planar platinum(II) moieties to slide some extent away from one another so as to afford long Pt···Pt distance (> 3.5 ), thus lacking metallophilic contact. As indicated in Figure 1 ( Figure S10, Supporting Information), 3·0.5 CH 2 ClCH 2 Cl ( Figure S11, Supporting Information), and 4·0.5 CH 2 ClCH 2 Cl (Figure 1 c), the planar platinum(II) complexes display two differently directed stacking motifs with almost mutually perpendicular orientations, in which each two adjacent planar platinum(II) moieties are antiparallel packed with the Pt···Pt distance being 3.504 (6) Solvate molecules are inserted into the crystal lattices and associated with the platinum(II) moieties through ClC À H···pA C H T U N G T R E N N U N G (C C) and/or CH 2 Cl···H À C (C CC 6 H 4 F) hydrogen bonds as shown in Figures S9-S14 (Supporting Information).…”

Section: Resultsmentioning

confidence: 99%

“…A significant redshift of the low-energy absorption band for the ground sample or vapochromic species 4·0.5 CH 2 Cl 2 is likely correlated with the shortened Pt···Pt distances and thus the increased Pt-Pt interactions (vide infra). [11,19,39] With excitation at 350 < l ex < 520 nm, complexes 2-4 displays bright orange-red luminescence at 608 nm for 2, 603 nm for 3, and 620 nm for 4 ( Figure S15, Supporting Information) with sub-microsecond range of emissive lifetimes in dichloromethane (Table 1). Large Stokes shifts together with long lifetimes reveal their phosphorescence character in triplet excited states.…”

Section: Resultsmentioning

confidence: 99%

“…5,5'-Bis(trimethylsilylethynyl)-2,2'-bipyridine (Me 3 SiCCbpyCCSiMe 3 ), 1-ethynyl-2-fluorobenzene (HCCC 6 H 4 F-2), 1-ethynyl-3-fluorobenzene (HCCC 6 H 4 F-3), and 1-ethynyl-4-fluorobenzene (HCCC 6 H 4 F-4), and Pt(Me 3 SiCCbpyCCSiMe 3 )Cl 2 were prepared by synthetic procedures described in literatures. [39,48] Other reagents were purchased from commercial sources and used as received unless stated otherwise. 1 H NMR and spectra were measured on a Bruker Avance 400 (400 MHz) spectrometer with SiMe 4 as the internal reference.…”

Section: Methodsmentioning

confidence: 99%

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Vapor‐ and Mechanical‐Grinding‐Triggered Color and Luminescence Switches for Bis(σ‐fluorophenylacetylide) Platinum(II) Complexes

Zhang

et al. 2011

Chemistry A European J

Self Cite

189

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Square-planar bis(σ-fluorophenylacetylide) platinum(II) complexes [Pt(Me(3)SiC≡CbpyC≡C-SiMe(3))(C≡CC(6)H(4)F)(2)] (C≡CC(6)H(4)F-2 for 2, C≡CC(6)H(4)F-3 for 3, and C≡CC(6)H(4)F-4 for 4; Me(3)SiC≡CbpyC≡CSiMe(3)=5,5'-bis(trimethylsilylethynyl)-2,2'-bipyridine) were prepared and were characterized by spectroscopic and luminescence studies, and X-ray crystallography. The color and luminescence of crystalline complex 3 is specifically sensitive to CHCl(3) vapor to afford 140-180 nm of luminescence vapochromic redshift, which is useful for specific detection of CHCl(3) vapor. Complex 4 displays selective luminescence vapochromic properties to CH(2)Cl(2) and CHCl(3) vapors with a luminescence vapochromic shift response of ca. 150-200 nm. Interestingly, complexes 2-4 exhibit reversible, and naked-eye perceivable, mechanical stimuli-responsive color and luminescence changes. When solid species 2-4 are crushed gently or ground, the crystalline state is converted to an amorphous phase. Meanwhile, bright yellow-orange luminescence in the crystalline species is converted to dark red under UV light irradiation with 100-160 nm of mechanochromic shift response. A vapochromic or mechanochromic cycle was monitored by dynamic variations in emission spectra and X-ray diffraction (XRD) patterns. The halohydrocarbon vapor- or mechanical-grinding-triggered color and luminescence switches are most likely correlated to a shorted intermolecular Pt-Pt distance as that revealed in vapochromic species 4·0.5 CH(2)Cl(2) by X-ray crystallography, thus leading to an increased contribution from intermolecular Pt-Pt interaction as demonstrated by DTF computational studies.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

See 2 more Smart Citations

Vapor‐ and Mechanical‐Grinding‐Triggered Color and Luminescence Switches for Bis(σ‐fluorophenylacetylide) Platinum(II) Complexes

Zhang

et al. 2011

Chemistry A European J

Self Cite

189

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“…5) were observed in deoxygenated CH 2 Cl 2 at room temperature upon the excitation at 425 nm, but the emission intensities of platinum compounds, Pt1 and Pt2, were very weak. These emissions were assigned to a triplet MLCT as the main element, including the interligand transition (LLCT) as the minor element, according to a photophysical study that Chen's group conducted with similar platinum bipyridine compounds [23,24]. The quantum yield (/ em = 0.013) of the emission of Pt1 is higher than that (/ em = 0.008) of Pt2, and this tendency is consistent with the luminescence of the corresponding ruthenium complexes.…”

Section: Photophysical Propertiesmentioning

confidence: 78%

Synthesis and photophysical characterization of ruthenium(II) and platinum(II) complexes with bis-pyridylethynyl-phenanthroline ligands as a metalloligand

Shiotsuka

Ueno

Asano

et al. 2015

Transition Met Chem

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Novel ruthenium complexes Ru(L)(bpy) 2 (PF 6 ) 2 and platinum organometallic complexes Pt(L)(-:-C 6-H 5 CH 3 ) 2 with bis-(pyridinyl)ethynyl-phenanthrolines (L = 3,8-bis[2-(3-pyridinyl)ethynyl]-1,10-phenanthroline or 3, 8-bis[2-(4-pyridinyl)ethynyl]-1,10-phenanthroline) that function as metalloligands by extra pyridyl units have been prepared using respective synthetic methods. These complexes have broad absorption bands assignable to the MLCT band as the main contributing factor in the 400 to 550 nm wavelength region. Furthermore, these complexes show phosphorescence centered around 680 nm upon excitation at 425 nm. These emissions were assigned to a triplet MLCTbased luminescence for the ruthenium complexes, while a triplet MLCT as the main element, including the interligand charge transfer as the minor element, was assigned for the platinum organometallic complexes. The quantum yields of the emission of the present ruthenium complexes were relatively high, and these complexes are exactly phosphorescent dyes, although the emission intensities of the platinum complexes are poor. These two types of complexes are capable of selective photophysical detection of some metal ions and can serve as metalloligands in the construction of supramolecular metallocycles.

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Vapochromic and Mechanochromic Tetrahedral Gold(I) Complexes Based on the 1,2‐Bis(diphenylphosphino)benzene Ligand

Osawa

Kawata

Igawa

et al. 2010

Chemistry A European J

118

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Tetrahedral gold(I) complexes containing the diphosphane ligand (dppb=1,2-bis(diphenylphosphino)benzene), [Au(dppb)(2)]X [X=Cl (1), Br (2), I (3), NO(3) (4), BF(4) (5), PF(6) (6), B(C(6)H(4)F-4)(4) (7)], and the ethanol and methanol adducts of complex 4, 8, and 9, were prepared to analyze their unique photophysical properties. These complexes are classified into two categories on the basis of their crystal structures. In Category I, the complexes (1-5) have relatively-small counter anions and two dppb ligands are symmetrically coordinated to the central Au(I) atom, and display an intense blue phosphorescence. Alternatively, the complexes (6-9) in Category II have large counter anions and two dppb ligands asymmetrically coordinated to Au(I) atom, and display a yellow or yellow orange phosphorescence. The difference in the phosphorescence color of the complexes between the Category I and II is ascribed to the change in the structure of the cationic moiety in the complex. According to DFT calculations, the symmetry reduction caused by the large counter anion of the complex in Category II gives the destabilization of HOMO (σ*) levels, leading to the red-shift of the emission peak. We have demonstrated that the symmetry reductions are responsible for the phosphorescence color alteration caused by external stimuli (volatile organic compounds and mechanical grinding).

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Luminescence Vapochromism of a Platinum(II) Complex for Detection of Low Molecular Weight Halohydrocarbon

Cited by 82 publications

References 69 publications

Vapor‐ and Mechanical‐Grinding‐Triggered Color and Luminescence Switches for Bis(σ‐fluorophenylacetylide) Platinum(II) Complexes

Vapor‐ and Mechanical‐Grinding‐Triggered Color and Luminescence Switches for Bis(σ‐fluorophenylacetylide) Platinum(II) Complexes

Synthesis and photophysical characterization of ruthenium(II) and platinum(II) complexes with bis-pyridylethynyl-phenanthroline ligands as a metalloligand

Vapochromic and Mechanochromic Tetrahedral Gold(I) Complexes Based on the 1,2‐Bis(diphenylphosphino)benzene Ligand

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