Aryl Diisocyanide Organometallic Coordination Polymers

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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Aryl Diisocyanide Organometallic Coordination Polymers

Cited by 6 publications

References 54 publications

Introduction to Photophysics and Photochemistry

Introduction to Photophysics and Photochemistry

Luminescent Organometallic Coordination Polymers Built on Isocyanide Bridging Ligands

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

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Aryl Diisocyanide Organometallic Coordination Polymers

Cited by 6 publications

References 54 publications

Introduction to Photophysics and Photochemistry

Introduction to Photophysics and Photochemistry

Luminescent Organometallic Coordination Polymers Built on Isocyanide Bridging Ligands

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

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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