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

Clément, Sébastien; Aly, Shawkat M.; Gagnon, Karl; Abd‐El‐Aziz, Alaa S.; Knorr, Michael; Harvey, Pierre D.

doi:10.1007/s10904-007-9176-6

Cited by 9 publications

(4 citation statements)

References 37 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The A-frame-containing metallopolymer 8 was synthesized by Cle ´ment et al; 148 taking advantage of the site-selectivity in ligand binding on the Pt center of the bimetallic ClPd(m-dppm) 2 -PtCl precursor, it was possible to introduce this particular structural motive into a (rather poorly soluble) coordination polymer (Scheme 11). The structure of 8 was verified by comparison of the available analytical data to those of analogous small-molecule model complexes.…”

Section: Metallo-supramolecular Polymers Based On Coordinative Bindingmentioning

confidence: 99%

Synthesis and characterization of metallo-supramolecular polymers

2016

View full text Add to dashboard Cite

The incorporation of metal centers into the backbone of polymers has led to the development of a broad range of organometallic and coordination compounds featuring properties that are relevant for potential applications in diverse areas of research, ranging from energy storage/conversion to bioactive or self-healing materials. In this review, the basic concepts and synthetic strategies leading to these types of materials as well as the scope of available characterization techniques will be summarized and discussed.

show abstract

Section: Metallo-supramolecular Polymers Based On Coordinative Bindingmentioning

confidence: 99%

Synthesis and characterization of metallo-supramolecular polymers

2016

View full text Add to dashboard Cite

show abstract

“…In view of the interesting properties observed for the A-frame dinuclear platinum alkynyl complexes as well as the potential applications of the A-frame dinuclear complexes as photonic materials, and multicentered reagents and catalysts, a computational study on a series of the A-frame alkynyl complexes was pursued to investigate their structural geometry, nature of electronic absorption and emission, as well as the possible mechanisms for the fluxional processes. In terms of the structural geometry, it is interesting to note that an intramolecular Pt···Pt distance of 3.236 Å was observed in the X-ray crystal structure of 2 , where the bridging alkynyl ligand unsymmetrically binds to the two metal centers, while a shorter Pt···Pt distance (2.903 Å) was found for the complex [Pt 2 (μ-dppm) 2 (μ-CCC 6 H 4 n Bu- p )(CCC 6 H 4 n Bu- p ) 2 ] + , where the bridging alkynyl ligand symmetrically binds to the two metal centers .…”

Section: Introductionmentioning

confidence: 99%

Computational Studies on the Photophysical Properties and NMR Fluxionality of Dinuclear Platinum(II) A-Frame Alkynyl Diphosphine Complexes

Lam

Yam

2010

Inorg. Chem.

View full text Add to dashboard Cite

The structural geometry, electronic structure, photophysical properties, and the fluxional behavior of a series of A-frame diplatinum alkynyl complexes, [Pt(2)(μ-dppm)(2)(μ-C≡CR)(C≡CR)(2)](+) [R = (t)Bu (1), C(6)H(5) (2), C(6)H(4)Ph-p (3), C(6)H(4)Et-p (4), C(6)H(4)OMe-p (5); dppm = bis(diphenylphosphino)methane], have been studied by density functional theory (DFT) and time-dependent TD-DFT associated with conductor-like polarizable continuum model (CPCM) calculations. The results show that the Pt···Pt distance strongly depends on the binding mode of the alkynyl ligands. A significantly shorter Pt···Pt distance is found in the symmetrical form, in which the bridging alkynyl ligand is σ-bound to the two metal centers, than in the unsymmetrical form where the alkynyl ligand is σ-bound to one metal and π-bound to another. For the two structural forms in 1-5, both the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) energy levels show a dependence on the nature of the substituents attached to the alkynyl ligand. The energies of the HOMO and LUMO are found to increase and decrease, respectively, from R = (t)Bu to R = Ph and to R = C(6)H(4)Ph-p, because of the increase of the π- conjugation of the alkynyl ligand. On the basis of the TDDFT/CPCM calculations, the low-energy absorption band consists of two types of transitions, which are ligand-to-ligand charge-transfer (LLCT) [π(alkynyl) → σ*(dppm)]/metal-centered MC [dσ*(Pt(2)) → pσ(Pt(2))] transitions as well as interligand π → π* transition from the terminal alkynyl ligands to the bridging alkynyl ligand mixed with metal-metal-to-ligand charge transfer MMLCT [dσ*(Pt(2)) → π*(bridging alkynyl)] transition. The latter transition is lower in energy than the former. The calculation also indicates that the emission for the complexes originates from the triplet interligand π(terminal alkynyls) → π*(bridging alkynyl)/MMLCT [dσ*(Pt(2)) → π*(bridging alkynyl)] excited state. In terms of the fluxional behavior, calculations have been performed to study the details of the mechanisms for the three fluxional processes, which are the σ,π-alkynyl exchange, the ring-flipping, and the bridging-to-terminal alkynyl exchange processes.

show abstract

“…We also recently reported the first A-frame-containing organometallic/coordination polymer arising from the reaction between the corresponding d 9 −d 9 MM′-bonded complex (M = Pd, M′ = Pt) and the 1,2-bis-(2-isocyanophenoxy)ethane assembling ligand. The material is found to be strongly luminescent at 77K …”

Section: Introductionmentioning

confidence: 99%

“…The material is found to be strongly luminescent at 77K. 9 We now wish to report the chemical and photophysical properties of homodinuclear Pd-Pd and Pt-Pt complexes containing PCP-NC (Chart 2). The PCP-NC ligand was chosen because the PCP-containing compounds exhibit luminescence.…”

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

Self Cite

View full text Add to dashboard Cite

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.

show abstract

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

Cited by 9 publications

References 37 publications

Synthesis and characterization of metallo-supramolecular polymers

Synthesis and characterization of metallo-supramolecular polymers

Computational Studies on the Photophysical Properties and NMR Fluxionality of Dinuclear Platinum(II) A-Frame Alkynyl Diphosphine Complexes

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

Contact Info

Product

Resources

About

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

Cited by 9 publications

References 37 publications

Synthesis and characterization of metallo-supramolecular polymers

Synthesis and characterization of metallo-supramolecular polymers

Computational Studies on the Photophysical Properties and NMR Fluxionality of Dinuclear Platinum(II) A-Frame Alkynyl Diphosphine Complexes

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

Contact Info

Product

Resources

About

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