Fluorescence properties of 1-(silylethynyl)naphthalenes and 1,4-bis(silylethynyl)naphthalenes in solutions, thin films and solid states

Maeda, Hideaki; Fujii, Tatsuzo; Minamida, Keita; Mizuno, Kazuhiko

doi:10.1016/j.jphotochem.2017.04.005

Cited by 8 publications

(3 citation statements)

References 33 publications

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“…The bis(ethynyl)-functionalized benzo[2,1,3]thiadiazole and naphthalene required for synthesizing Ru 2 BTD and Ru 2 NA were accessible by Sonogashira coupling of 4,7dibromo-benzo [2,1,3]thiadiazole or 1,4-dibromonaphthalene with Me 3 Si−CCH (TMSA) and subsequent removal of the Me 3 Si (TMS) protecting groups with K 2 CO 3 in MeOH/ THF. 40,41 While Ru 2 BTD could be obtained in 91% yield by reaction of the dialkyne with 2 equiv of HRu(CO)Cl(P i Pr 3 ) 2 at r.t., 2-fold hydroruthenation of the diethynylated naphthalene precursor required an elevated temperature of 50 °C and a reaction time of several hours. Such a difference in reactivity is rooted in unfavorable steric interactions between the hydrogen atoms in positions 5 and 8 with the β-vinylic protons of the vinyl ruthenium moiety (Figure 1).…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…1 H NMR (800 MHz) and 13 C (202 MHz) NMR spectra were recorded on a Bruker Avance Neo 800 spectrometer. 2,1,3-Benzothiadiazole, 100 4,7-dibromo-2,1,3-benzothiadiazole, 101 4,7diethynyl-2,1,3-benzothiadiazole, 40 and 1,4-diethynylnaphthalene 41 were prepared according to literature procedures. The supporting electrolyte NBu 4 + [B{C 6 H 3 (CF 3 ) 2 -3,5} 4 ] − was synthesized in a twostep procedure starting from 3,5-bis(trifluoromethyl)-bromobenzene to first give Na + [B{C 6 H 3 (CF 3 ) 2 -3,5} 4 ] − , 102 which was subsequently subjected to a cation exchange reaction.…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

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Influence of Quinoidal Distortion on the Electronic Properties of Oxidized Divinylarylene-Bridged Diruthenium Complexes

2019

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We present four new divinylarylene-bridged diruthenium complexes of the type {Ru(CO)Cl(P i Pr3)2}2(μ-CHCH–Ar–CHCH) with naphthalene-1,4-diyl (Ru 2 NA), 2,1,3-benzothiadiazole (Ru 2 BTD), bis(benzothiadiazolyl)ethene (Ru 2 v BTD 2 ), or bis(benzothiadiazolyl)ethyne (Ru 2 e BTD 2 ) as the arylene units. The radical cations of the complexes with shorter arylene bridges are intrinsically valence-delocalized on the IR time scale. In contrast to phenylene-bridged [{Ru(CO)Cl(P i Pr3)2}2(μ-CHCH–C6H4-1,4-CHCH)]2+ (Ru 2 -p-phen 2+ ), the dioxidized forms of complexes Ru 2 BTD and Ru 2 NA are electron paramagnetic resonance (EPR) silent. Replacing the E-stilbenediyl linker of the complex {Ru(CO)Cl(P i Pr3)2}2(μ-CHCH–C6H4–CHCH–C6H4–CHCH) (Ru 2 v p-phen 2 ) by vBTD2 or eBTD2 enhances electronic coupling and charge delocalization of their one-electron-oxidized mixed-valent forms. While the latter radical cations are still charge-localized species on the IR time scale, they are fully delocalized on the slower EPR time scale. As a token of a quinoidally distorted bridge, Ru 2 e BTD 2 2+ features a characteristic IR stretch of a cumulenic CCCC increment. For compound Ru 2 v BTD 2 , rearrangement to a quinoidal structure is manifested through potential inversion (i.e., the half-wave potential of the second oxidation is lower than that of the 0/1+ redox couple) in the CH2Cl2/NBu4BArF electrolyte. The BTD complexes are intensely colored in their neutral states and exhibit strong NIR absorptions of their radical cations as well as of their dioxidized forms.

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Section: ■ Results and Discussionmentioning

confidence: 99%

Section: ■ Experimental Sectionmentioning

confidence: 99%

Influence of Quinoidal Distortion on the Electronic Properties of Oxidized Divinylarylene-Bridged Diruthenium Complexes

2019

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“…As revealed by the X‐ray diffraction analysis, the small plane‐to‐plane separation of ≈3.31 Å for H‐Pt and ≈3.22 Å for tBu‐Pt indicate the strong π–π interaction, and the large d Pt–Pt of 4.663(4) Å for H‐Pt and 4.8920(8) Å for tBu‐Pt confirm the absence of Pt‐Pt interaction, therefore, the bright emissions peaking at 620 and 708 nm for H‐Pt neat film and tBu‐Pt neat film, respectively, can be ascribed to the excimeric emissions. Because the formation of excimers could quench the luminescence, thus H‐Pt and tBu‐Pt in neat films showed decreased PLQYs compared with those in solutions. However, the d Pt–Pt of 3.3752(7) Å is small enough to result in significant Pt–Pt interaction, thus the greatly red‐shifted emission of F‐Pt neat film could be induced by the MMLCT transition .…”

Section: Methodsmentioning

confidence: 99%

Enhancing Molecular Aggregations by Intermolecular Hydrogen Bonds to Develop Phosphorescent Emitters for High‐Performance Near‐Infrared OLEDs

Yang

Guo

et al. 2019

Advanced Science

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Phosphorescent near‐infrared (NIR) organic light‐emitting devices (OLEDs) have drawn increasing attention for their promising applications in the fields such as photodynamic therapy and night‐vision readable displays. Here, three simple phosphorescent Pt(II) complexes are synthesized, and their intermolecular interactions are investigated in crystals and neat films by X‐ray single crystal diffraction and grazing‐incidence wide‐angle X‐ray scattering, respectively. The photophysical properties, molecular aggregation (including Pt–Pt interaction), molecular packing orientation, and electron transport ability are all influenced by the strong intermolecular hydrogen bonds. Consequently, the nondoped OLEDs based on tBu‐Pt and F‐Pt show electroluminescent emissions in NIR region with the highest external quantum efficiencies of 13.9% and 16.7%, respectively.

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Interfacial Self‐Assembly of Closely Packed Nanoparticle Arrays of Silica@Multiporphyrin Hybrids as Light‐Sensitizers for Dye Degradation and Viologen Photochromism

Wang

Chen

et al. 2019

Chemistry An Asian Journal

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Light‐sensitizer functionalized organic–inorganic hybrid materials have attracted much attention owing to their potential applications in the fields of optoelectronics, heterogeneous catalysis, sensors, and nanotechnology. Here, an interfacial self‐assembly of zero‐dimensional (0D) silica@multiporphyrin array nanohybrids and their 3D Langmuir–Blodgett (LB) films is reported. Photoactive tetrapyridylporphyrin (TPyP) was first assembled on the silica nanoparticles’ surfaces via silane, substitution, and coordination reactions to produce nanoSiO2@(Pd‐TPyP)n hybrids. Then, the Cd2+‐nanoSiO2@(Pd‐TPyP)n monolayers and LB films were constructed on the CdCl2 subphase surface. These monolayers and LB films displayed stronger stability, as well as more uniform and closely packed nanoparticle arrays compared with those prepared on the pure water surface, owing to the formation of strong network‐like Pd‐ and Cd‐TPyP coordination units, which significantly enhanced the nanoparticles’ interaction. Further, compared with that of the 0D nanoSiO2@(Pd‐TPyP)n hybrids, the degradation efficiency was nearly 20 times higher when the hybrids’ LB films were used as light‐sensitizers for the photocatalytic degradation of RhB. Finally, flexible photochromic devices were constructed by using the LB films sandwiched between two electrodes, which displayed a reversible photoinduced redox reaction of viologen together with a color change process. Because TPyP was strongly immobilized on the nanoparticles’ surfaces and the particles were connected through the Py‐Pd2+‐Py and Py‐Cd2+‐Py coordination units with the 3D network‐like architecture, the present nanohybrids and LB films had good stability and reusability.

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Fluorescence properties of 1-(silylethynyl)naphthalenes and 1,4-bis(silylethynyl)naphthalenes in solutions, thin films and solid states

Cited by 8 publications

References 33 publications

Influence of Quinoidal Distortion on the Electronic Properties of Oxidized Divinylarylene-Bridged Diruthenium Complexes

Influence of Quinoidal Distortion on the Electronic Properties of Oxidized Divinylarylene-Bridged Diruthenium Complexes

Enhancing Molecular Aggregations by Intermolecular Hydrogen Bonds to Develop Phosphorescent Emitters for High‐Performance Near‐Infrared OLEDs

Interfacial Self‐Assembly of Closely Packed Nanoparticle Arrays of Silica@Multiporphyrin Hybrids as Light‐Sensitizers for Dye Degradation and Viologen Photochromism

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