The title compound 4 was synthesized from dipotassium 1,8‐anthracenedisulfonate (9) and potassium diphenylphosphide (Ph<sub>2</sub>PK). On reaction of 4 with nickel(II) chloride and bis‐(benzonitrile)palladium(II) chloride, cyclometallation of the C – H bond in anthracene 9‐position led to the square‐planar chelate complexes 11 and 13, respectively. In the case of the palladium complex 13, the cyclometallated structure was proved by X‐ray structure analysis. Treatment with aqueous potassium cyanide did not

Haenel, Matthias W.; Jakubik, Dieter; Krüger, Carl; Betz, P.

doi:10.1002/cber.19911240214

Cited by 52 publications

(15 citation statements)

References 23 publications

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“…[1‐PPh 2 ‐(C 14 H 9 )] was synthesized from 1‐chloroanthracene via nucleophilic substitution with lithium diphenylphosphanide similar to reported procedures for the 1,8‐bis(diphenylphosphane)anthracene ( Scheme ). [ 31 ] After aqueous workup, the phosphane was obtained in good yields and single crystals suitable for structure determination were obtained by recrystallization from dichloromethane (DCM). The compound crystallizes in the triclinic space group P

\overset{1}{true}

with one molecule in the asymmetric unit.…”

Section: Resultsmentioning

confidence: 99%

Insights into Excimer Formation Factors from Detailed Structural and Photophysical Studies in the Solid‐State

Schillmöller

Herbst‐Irmer

2021

Advanced Optical Materials

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Opposite behavior with an emission enhancement upon aggregation of the fluorophores is also known, but early reports are rare. [7] This phenomenon is coined aggregationinduced-emission (AIE) and became more popular through the work of Tang and co-workers since the early 2000s. [7,8,9] A plethora of molecules with AIE-behavior was investigated and a general understanding of their photophysical properties was achieved. [10,11] The emission quenching is referred to internal motion of suitable substituents like tetra phenylethylene and hexaphenylsilole at the fluorophore. [6,12] Rotation and vibration of these groups open non-radiative pathways which result in radiationless decay in solution. [9,13] Aggregation confines the flexibility of the substituents to restrict the internal motion. [14] Consequently, the non-radiative pathways are blocked, and the emission enhances in highly aggregated-solutions and in the solidstate. [11,15] Further strategies for obtaining solid-state luminescent materials aim at the introduction of bulky substituents at the fluorophores to prevent strong interchromophoric interactions. [16] These approaches are mainly based on intramolecular modifications and therefore the resulting fluorescence of the aggregates can be considered to be close to the emission from a monomeric state of the fluorophores.Controlling photophysical properties through non-covalent interactions (NCIs) [17] is more challenging. In early works, Jelley and Scheibe observed the appearance of new absorption and emission bands in pseudoisocyanine solutions with increasing dye-concentration, which were attributed to the formation of aggregates. [18] More recently a different approach for controlling and optimizing the photophysical properties of polyaromatic hydrocarbons in the solid-state has been successfully introduced. Instead of avoiding intermolecular interactions, molecules are designed, which allow specific interactions between their fluorophores in the aggregated state. The occurring π-π interactions lead to the formation of an excited dimer (excimer) after irradiation. [19] The formation of excimers in solution is well known since the investigations of the pyrene excimer by Förster [20] and Birks. [21] The typical features of spectral broadening and increased lifetime are also well investigated. In recent publications, this approach was successfully transferred to efficient solid-state emitters. Through control of the NCIs, the formation of excimers or exciplexes in the solid-state is possible and allows tuning of the photophysical properties. [22][23][24][25][26] Solid-state luminescent materials are essential for the development of optoelectronic devices like lasers, sensors, and organic light-emitting diodes. Organic molecules reveal several benefits like stability, costs, and environmental compatibility compared to metal-based materials. As common organic fluorophores often suffer from aggregation-caused quenching, different strategies have been established to overcome this quenching, which are mainly based...

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\overset{1}{true}

with one molecule in the asymmetric unit.…”

Section: Resultsmentioning

confidence: 99%

Insights into Excimer Formation Factors from Detailed Structural and Photophysical Studies in the Solid‐State

Schillmöller

Herbst‐Irmer

2021

Advanced Optical Materials

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“…In the ionic complex the Xantphos ligand coordinates in the same fashion as 1,8-bis(diphenylphosphino)anthracene. 49 The phosphorus atoms are trans-coordinated (P-Pd-P angle = 165.15(2)Њ) and the Pd-P distances of both phosphorus atoms are similar (Pd-P1 = 2.2912(6) and Pd-P2 = 2.2816(6) Å). The oxygen atom of the Xantphos ligand is coordinated to the metal centre (Pd-O distance = 2.1537(14) Å).…”

Section: -45mentioning

confidence: 98%

The coordination behaviour of large natural bite angle diphosphine ligands towards methyl and 4-cyanophenylpalladium(ii) complexes

Zuideveld

Swennenhuis

Boele

et al. 2002

J. Chem. Soc., Dalton Trans.

148

120

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The structures of neutral and ionic 4-cyanophenylpalladium() and methylpalladium() complexes containing bidentate phosphine ligands were investigated in solution and in the solid state. Diphosphine ligands with a xanthene and a ferrocene backbone were used. New bis(dialkylphosphino) substituted Xantphos ligands were synthesised. 1 H NMR and31 P NMR spectroscopy, conductivity measurements, UV-Vis spectroscopy, and X-ray crystallography were used to elucidate the structures of the complexes. Subtle changes of the phosphine ligands govern the coordination mode of the ligand. A variety of bidentate cis-, and trans-coordination and terdentate P-O-P, P-S-P and P-Fe-P coordination modes of the ligands were observed.

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“…we reported the synthesis of the 1,8bis(diphenylphosphino)anthracene (1) and its reaction with nickel or palladium dichloride forming cyclometallated and hence extremely stable complexes 2 and 3. 2 As a result of the cyclometallation at the anthracene C-9 atom, the diphosphine 1 is acting as a tridentate PCP ligand in these complexes. Whereas we first had failed to prepare the diphosphine 1 from either 1,8-dichloro-or 1,8-dibromoanthracene, 1 was obtained in moderate yield of 33 % by reaction of potassium anthracenedisulfonate (4) with two equivalents potassium diphenylphosphide (Ph 2 PK) in diethylene glycol diethyl ether (DEGDEE) under harsh reaction conditions (180°C, 20 h).…”

Section: Previouslymentioning

confidence: 99%

“…Whereas we first had failed to prepare the diphosphine 1 from either 1,8-dichloro-or 1,8-dibromoanthracene, 1 was obtained in moderate yield of 33 % by reaction of potassium anthracenedisulfonate (4) with two equivalents potassium diphenylphosphide (Ph 2 PK) in diethylene glycol diethyl ether (DEGDEE) under harsh reaction conditions (180°C, 20 h). 2,3 The disulfonate 4 needed for this conversion was prepared by zinc reduction of potassium 9,10-anthraquinone-1,8-disulfonate. 4 However, since the latter compound apparently is not commercially available anymore, it was desirable to search for a new and improved synthesis of the diphosphine 1.…”

Section: Previouslymentioning

confidence: 99%

Facile Syntheses of 1,8-Bis(diphenylphosphino)anthracene and 1,8-Bis(dimethylamino)anthracene by Nucleophilic Substitution of 1,8-Difluoroanthracene

Haenel¹,

Oevers²,

Bruckmann³

et al. 1998

Synlett

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1,8-Bis(diphenylphosphino)anthracene (1) was prepared in a three-step synthesis in 51 % overall yield starting from 1,8-dichloro-9,10-anthraquinone (8). Compound 8 was converted by chlorinefluorine exchange and reduction with zinc into 1,8-difluoroanthracene (7) from which 1 was obtained by reaction with potassium diphenylphosphide. The conversion of 7 with lithium dimethylamide to 1,8-bis(dimethylamino)anthracene (10) clearly showed that in the case of 7 direct nucleophilic displacement (addition-elimination mechanism) dominates over aryne formation (elimination-addition mechanism). Single crystal X-ray structure analyses are reported for 1 and 10. Previouslywe reported the synthesis of the 1,8-bis(diphenylphosphino)anthracene (1) and its reaction with nickel or palladium dichloride forming cyclometallated and hence extremely stable complexes 2 and 3. 2 As a result of the cyclometallation at the anthracene C-9 atom, the diphosphine 1 is acting as a tridentate PCP ligand in these complexes. Whereas we first had failed to prepare the diphosphine 1 from either 1,8-dichloro-or 1,8-dibromoanthracene, 1 was obtained in moderate yield of 33 % by reaction of potassium anthracenedisulfonate (4) with two equivalents potassium diphenylphosphide (Ph 2 PK) in diethylene glycol diethyl ether (DEGDEE) under harsh reaction conditions (180°C, 20 h). 2,3 The disulfonate 4 needed for this conversion was prepared by zinc reduction of potassium 9,10-anthraquinone-1,8-disulfonate. 4 However, since the latter compound apparently is not commercially available anymore, it was desirable to search for a new and improved synthesis of the diphosphine 1.In a recent paper we described the reaction of 4,5-difluoroacridine (5) with potassium diphenylphosphide (Ph 2 PK) giving 4,5-bis(diphenylphosphino)acridine (6) in 79 % yield. 5 This prompted us to attempt the synthesis of 1 from 1,8-difluoroanthracene (7) and to investigate the use of fluoro substituted polycyclic aromatic hydrocarbons in nucleophilic aromatic substitution reactions with alkali metal phosphides and other nucleophiles. 6The unknown 1,8-difluoroanthracene (7) was prepared from the commercially available 1,8-dichloro-9,10-anthraquinone (8) in a twostep synthesis. Following a literature procedure 8 was converted by reaction with cesium fluoride in dimethyl sulfoxide under anhydrous conditions into 1,8-difluoro-9,10-anthraquinone (9) [m.p. = 228°C (DSC, lit. 7 m.p. = 228-229°C), 71 %]. 7 Reduction of 9 with zinc powder in aqueous ammonia (75°C, 4 h) followed by an acidic treatment (aqueous HCl, 2-propanol, reflux, 3 h) yielded 7 [yellow needles, m.p. = 142°C (DSC), 84%]. 8,9 As anticipated compound 7 proved to be highly reactive for nucleophilic displacement of the fluoro substituents by alkali metal phosphides. Reaction with two equivalents potassium diphenylphosphide (Ph 2 PK, dioxane/THF 5:1 reflux, 3 h) 10 converted 7 in excellent yield to the diphosphine 1 [yellow needles, m.p. = 234°C (lit. 2 m.p. = 233-235°C), 86 %]. For the three-step synthesis starting from commercial 8...

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Cited by 52 publications

References 23 publications

Insights into Excimer Formation Factors from Detailed Structural and Photophysical Studies in the Solid‐State

Insights into Excimer Formation Factors from Detailed Structural and Photophysical Studies in the Solid‐State

The coordination behaviour of large natural bite angle diphosphine ligands towards methyl and 4-cyanophenylpalladium(ii) complexes

Facile Syntheses of 1,8-Bis(diphenylphosphino)anthracene and 1,8-Bis(dimethylamino)anthracene by Nucleophilic Substitution of 1,8-Difluoroanthracene

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