Functional Linkers for Catalysis

Legrand, Alexandre; Canivet, J.; Farrusseng, David

doi:10.1002/9783527693078.ch12

Cited by 1 publication

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“…This field is dominated by ferrocenyl-, − (η 5 -cyclopentadienyl)metal-, and (η 6 -benzene)metal-containing pendant or linkage groups. − The commonly reported properties are, for instance, luminescence (also including near-IR emission), magneticity, catalysis, and recently theranostics. , Coordination polymers, , metal organometallic frameworks (MOMFs), , and nanocomposites, which are the entries to functional materials, have also been prepared using these types of ligands. Concurrently, the synthesis and investigations of other types of organometallic ligands were reported, and multiple functional materials, including MOMFs, − have been designed. One interesting class of organometallic ligands includes the platinum(II)-containing complexes, which are sometime reported to be highly emissive , and electrochromic .…”

Section: Introductionmentioning

confidence: 99%

A Platinum(II) Organometallic Building Block for the Design of Emissive Copper(I) and Silver(I) Coordination Polymers

2020

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The tritopic organometallic ligand trans-MeSC6H4CCPt(PMe3)2(CN) (L1) was prepared from cis-PtCl2(PMe3)2 and p-ethynyl(methyl thioether)benzene. Its versatility was shown with the formation of [CuX(L1)] n coordination polymers (CPs) with CuX salts in MeCN (X = I (CP1), CN (CP2), SCN (CP3)). These CPs were characterized by X-ray crystallography, thermal gravimetric analysis (TGA), and IR and Raman spectroscopy. CP1 consists of a 1D head-to-tail chain formed by tricoordinated −CN–CuI(η2-CC)– linkages, whereas CP2 is built upon a central (CuCN) n zigzag chain bearing dangling L1s held by −CN–Cu bonds. Finally, CP3 exhibits 2D sheets secured by Cu–NC–/–(Me)S–Cu bondings and transversal Cu–S–CN–Cu bridges. Concurrently, the CPs formed with AgX (X = NO3 – (CP4 and CP5), CF3CO2 – (CP6) PF6 – (CP7)) exhibits 2D sheets with guest molecules (anion, solvents) inside the tight pores or between layers. These new materials are emissive: L1 (λ0–0 ∼465 nm), CP1–CP7 (500 < λmax < 620 nm). Their photophysical properties (absorption and emission spectra, emission lifetimes (∼0.2 < τe < 120 μs), and quantum yields in the solid state at 77 and 298 K) were analyzed. The various natures of the emissive excited states were addressed by density functional theory (DFT) and time-dependent DFT (TDDFT) computations. For CP1, this state is a triplet halide or pseudohalide to ligand charge transfer 3XLCT (CT = charge transfer; X = I; L = L1) and for CP2, it is 3XLCT (X = CN; L = L1). However, for CP3, it is 3XLCT (X = SCN; L = L1). For CP4, the T1 state is described as a [MeSC6H4(η2-CC)-Ag(NO3)]2 → [Pt]/CCC6H4SMe CT.

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