The Spectroscopy and Photophysical Behavior of Diphosphine- and Diisocyanide-Containing Coordination and Organometallic Oligomers and Polymers: Focus on Palladium and Platinum, Copper, Silver, and Gold

Harvey, Pierre D.

doi:10.1007/978-0-387-72947-3_4

Cited by 3 publications

(4 citation statements)

References 59 publications

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“…For example, the commercial diphosphane Ph 2 P(CH 2 ) m PPh 2 ligands (m = 2-9) are well known for making coordination polymers. [1,2] Corresponding chiral versions of ligands similar to those presented in this work should lead to new crystal motifs and optical properties.…”

Section: Discussionmentioning

confidence: 90%

“…Although there is no change in emission maxima, due to the good similarity in chemical environment, the emission lifetime changes by a factor of 2. This change reflects the change in polymer structure ···Ag(diphos)Ag(diphos)··· vs. ···Ag(diphos) 2 Ag-(dmb)···. Similarly, the {Cu(dpppen)(CNtBu) 2 + } n and {Cu 2 (dppm) 2 (dmb) 2 2+ } n (20) exhibit emission lifetime of 42 and 24 μs, respectively.…”

Section: Introductionmentioning

confidence: 86%

“…[1,2] The most common diphosphane bridging ligands are those of the type Ph 2 P(CH 2 ) m PPh 2 with m = 1-6. The smallest of the series is bis(diphenylphosphanyl)methane (dppm), but one can also associate the structurally related bis(diphenylarsanyl)methane (dpam) and bis(dimethylphosphanyl)methane (dmpm).…”

Section: Introductionmentioning

confidence: 99%

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The First P‐Stereogenic 1D Coordination Polymers with the Metal Centers in the Backbone

et al. 2011

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The enantiomeric ligands (R,R)-and (S,S)-bis(o-anisylphenylphosphanyl)methane (R, R-22 and S,S-22) and (R,R)-and (S,S)-bis(phenyl-m-xylylphosphanyl)methane (R,R-23 and S,S-23; dppm*), were treated with [Cu(NCCH 3 ) 4 ](BF 4 ) and AgBF 4 to produce the binuclear complexes [Cu 2 (dppm*) 2 -(NCCH 3 ) 4 ](BF 4 ) 2 or [Ag 2 (dppm*) 2 ](BF 4 ) 2 , respectively. Then, these complexes were used as building blocks to prepare the first P-chirogenic 1D coordination polymers {[M 2 (dppm*) 2 -where M is part of the polymer backbone. In the absence of X-ray structure determination, 1 H NMR, chemical analysis, UV/Vis spectrometry, emission spectroscopy, and photophysical measurements were used to unambiguously demonstrate the isostructural nature of these new polymers with the parent dppm-containing polymers 20 and 21. [14] Results and DiscussionSyntheses and characterization. The stereoselective syntheses of the (R,R)-and the (S,S)-ligands 22 were performed in several steps using the (+)-or (-)-ephedrine methodology, via formation of the chlorophosphaneborane intermediate 26. [18] The key step of the synthesis is the methano bridge formation from the reaction of the carbanion derived from the methylphosphane-borane 27 with the chlorophosphane-borane 26; see Scheme 6, only the (R,R)-version is shown. [18] Thus, the reaction of the (S)-o-anisylchlorophenylphosphane-borane 26 with the MeLi reagent affords the corresponding (R)-methylphosphane-borane 27 with inversion of configuration at the P-centre. After deprotonation of the methylphosphane-borane 27 with nBuLi, reaction with the Scheme 5. Scheme 6.

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Section: Discussionmentioning

confidence: 90%

Section: Introductionmentioning

confidence: 86%

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The First P‐Stereogenic 1D Coordination Polymers with the Metal Centers in the Backbone

et al. 2011

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“…We reported the physicochemical properties of oligomeric and polymeric dppm-spanned Pd−Pd and Pt−Pt arrays assembled by unconjugated and conjugated diisocyanide ligands (Chart ). , The unconjugated polymers were those using the saturated dmb ligand (1,8-diisocyano- p -menthane), and the conjugated ones were built upon para -diisocyano-tetramethylbenzene. The conjugation was demonstrated by the red-shift of the absorption bands going from the monomeric models [M(μ-dppm) 2 (μ-CNC 6 H 4  i Pr) 2 M] 2+ (M = Pd, Pt) to the polymers and by the increased thermal stability in the polymers by comparison with the same models.…”

Section: Introductionmentioning

confidence: 99%

Probing the Electronic Communication of the Isocyanide Bridge Through the Luminescence Properties of the d⁹−d⁹ [ClPt(μ-dppm)₂Pt(C≡N—PCP)]⁺ and A-Frame [ClPd(μ-dppm)₂(μ-C═N—PCP)PdCl] Complexes

et al. 2008

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The homodinuclear d9-d9 ClM(mu-dppm)2MCl2 complexes, 1 (M ) Pt) and 2 (M ) Pd) react with the conjugated and luminescent PCP-NC ligand (3, PCP ) [2.2]paracyclophane) to provide the corresponding d9-d9 terminal[ClPt(mu-dppm)2Pt(CNsPCP)]Cl (4) and d8-d8 A-frame [ClPd(mu-dppm)2(mu-CdNsPCP)PdCl] (5) isocyanide complexes, respectively. These two bimetallic complexes were characterized by IR, 1H, and 31P{1H} NMR and bychemical analysis. IR data (nu(CN) bridging vs terminal) reveal a terminal isocyanide bonding mode for 4 (2147cm(-1)) and an A-frame structure for 5 (1616 cm(-1)). The optical and emission properties of the free isocyanide 3as well as those of the homodinuclear complexes 4 and 5 were studied by UV-visible and luminescence spectroscopy and by photophysical measurements. The unexpected presence of simultaneous intraligand pipi* fluorescence and phosphorescence attributable to the organic PCP-NC ligand, as well as luminescence from the inorganic M2-bonded Pt2(mu-dppm)2 center arising from a lower energy excited LMCT state (ligand-to-metal-charge-transfer) for4 at 77 K, indicates a weak conjugation between the two chromophores and an absence of efficient singlet andtriplet energy transfers. For 5, only the fluorescence and phosphorescence bands of the PCP-NC ligand are observed [since the A-frame XPd(mu-dppm)2(mu-L)PdX (L ) isocyanide, X ) halide) is not luminescent], stressing that the NtC bridge exhibits modest electronic communication properties.

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The First A-Frame-Containing Organometallic Polymer: Taking Advantage of the Site Selectivity in PdPt-Mixed Metal Bimetallics

Clément

Aly

Gagnon

et al. 2007

J Inorg Organomet Polym

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The Spectroscopy and Photophysical Behavior of Diphosphine- and Diisocyanide-Containing Coordination and Organometallic Oligomers and Polymers: Focus on Palladium and Platinum, Copper, Silver, and Gold

Cited by 3 publications

References 59 publications

The First P‐Stereogenic 1D Coordination Polymers with the Metal Centers in the Backbone

The First P‐Stereogenic 1D Coordination Polymers with the Metal Centers in the Backbone

Probing the Electronic Communication of the Isocyanide Bridge Through the Luminescence Properties of the d⁹−d⁹ [ClPt(μ-dppm)₂Pt(C≡N—PCP)]⁺ and A-Frame [ClPd(μ-dppm)₂(μ-C═N—PCP)PdCl] Complexes

The First A-Frame-Containing Organometallic Polymer: Taking Advantage of the Site Selectivity in PdPt-Mixed Metal Bimetallics

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The Spectroscopy and Photophysical Behavior of Diphosphine- and Diisocyanide-Containing Coordination and Organometallic Oligomers and Polymers: Focus on Palladium and Platinum, Copper, Silver, and Gold

Cited by 3 publications

References 59 publications

The First P‐Stereogenic 1D Coordination Polymers with the Metal Centers in the Backbone

The First P‐Stereogenic 1D Coordination Polymers with the Metal Centers in the Backbone

Probing the Electronic Communication of the Isocyanide Bridge Through the Luminescence Properties of the d9−d9 [ClPt(μ-dppm)2Pt(C≡N—PCP)]+ and A-Frame [ClPd(μ-dppm)2(μ-C═N—PCP)PdCl] Complexes

The First A-Frame-Containing Organometallic Polymer: Taking Advantage of the Site Selectivity in PdPt-Mixed Metal Bimetallics

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Probing the Electronic Communication of the Isocyanide Bridge Through the Luminescence Properties of the d⁹−d⁹ [ClPt(μ-dppm)₂Pt(C≡N—PCP)]⁺ and A-Frame [ClPd(μ-dppm)₂(μ-C═N—PCP)PdCl] Complexes