Organometallic and Coordination Polymers, and Linear and Star Oligomers Using the trans-Pt(PR3)2(C≡C)2 Linker

Harvey, Pierre D.

doi:10.1007/s10904-017-0673-y

Cited by 13 publications

(7 citation statements)

References 93 publications

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“…For triplet excited states, this phenomenon has also been observed for platinum(II)-containing organometallic conjugated polymers. 58,59 In these cases, the low-lying excited states are charge transfer ones originating from the conjugated chain (λ emi > 750 nm), whereas the upper triplet excited state, T n , stems from a localized state of the platinum(II) fragment (λ emi = 450 nm). Moreover, the short-excited state lifetime of this upper T n emission (<100 ps) in CP2 is also consistent with the generally rapid nonradiative depletion of the upper excited states.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

A Fused Poly(truncated rhombic dodecahedron)-Containing 3D Coordination Polymer: A Multifunctional Material with Exceptional Properties

et al. 2021

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The design of new and inexpensive metal-containing functional materials is of great interest. Herein is reported a unique thermochromic near-IR emitting coordination polymer, 3D-[Cu8I8(L1)2] n , CP2, which is formed when ArS(CH2)4SAr (L1, Ar = 4-C6H4OMe) reacts with 2 equiv of CuI in EtCN. In MeCN, CP1 ([Cu4I4(L1)(MeCN)2] n , consisting of an alternating [-Cu4I4-L1-Cu4I4-L1-] n chain where the Cu4I4 cubane units bear two metal-bound MeCN molecules, is formed. Heat-driven elimination of these MeCN’s in solid CP1 also leads to CP2 through a predisposed organization of the Cu4I4 units prone to fusion after MeCN eliminations (i.e., a rare case of template effect). The CP2 structure exhibits parallel 1D-(Cu8I8) n chains, (z-axis; designated 1D-[CuI] n ) as secondary building units (SBU) held together by parallel thioether ligands (x,y-axes), forming a nonporous 3D network. The structure of this 1D-[CuI] n SBU is unprecedented and consists of a series of fused and twisted open Cu4I4 cubanes forming a fused poly(truncated rhombic dodecahedron). Unexpectedly, the compact 3D CP2 exhibits a solid-to-solid phase transition at 100 °C and a hysteresis of ∼20 °C. CP1 emits intensively (298 K: λemi = 564 nm; Φe = 0.35), whereas CP2 presents a strongly red-shifted weaker emission (298 K: λemi ∼ 740 nm, Φe < 0.0001). Moreover, CP2, which is stable over long periods of time, exhibits thermochromism where the emission intensity of the near-IR band decreases significantly at the benefit of a ligand-centered phosphorescence at 415 nm. Altogether, these properties listed above make CP2 exceptional. The low-energy singlet and triplet excited states have been assigned to ligand/metal-to-ligand charge transfer based on DFT and TD-DFT computations.

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Section: ■ Results and Discussionmentioning

confidence: 99%

A Fused Poly(truncated rhombic dodecahedron)-Containing 3D Coordination Polymer: A Multifunctional Material with Exceptional Properties

et al. 2021

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“…A plethora of research has been conducted in academic and industrial laboratories around the globe in the last few decades to develop smart devices based on organic, inorganic, and hybrid materials. , In particular, for optoelectronic (O-E) applications, chemists have developed various π-conjugated systems, and among them, oligo-ynes, poly-ynes, and poly(metalla-ynes) have emerged as one of the archetypical candidates. − Low cost, lightweight, suitability for large area applications, possibility to process at low temperatures, mechanical flexibility, tunable photophysical and physicochemical properties, and unique capability to retain electronic and chemical properties of organic and metal frameworks are some of the intriguing features offered by this class of materials. These features make them suitable for application in nanoscale molecular wires, molecular magnets, optical filters, logic gates, liquid crystal displays, light-emitting diodes (LEDs), sensors, photovoltaic devices (PVs), field-effect transistors (FETs), sensing, catalysis, medicine, etc. − The occurrence of oligo- and poly-ynes in flora and fauna , as well as in interstellar materials richly justifies their unique and broad versatility. Moreover, they are regarded as model compounds of carbyne, a controversial allotropic form of carbon. − …”

Section: Introductionmentioning

confidence: 99%

“…Several reviews and books on the linear, starred, branched, and dendritic forms of this class of materials exist (Table ). ,,,− In this review, we focus on the synthesis, properties, and application of linear organic and organometallic oligo- and poly-ynes. Because of the large number of variants in this class of materials, we have restricted ourselves to linear (a) organic oligo- and poly-ynes and (b) organometallic oligo- and poly-ynes containing at least one M-C σ-bond with trans -alkynyl configuration around the metal center (few examples of cis-complexes have also been discussed).…”

Section: Introductionmentioning

confidence: 99%

Rise of Conjugated Poly-ynes and Poly(Metalla-ynes): From Design Through Synthesis to Structure–Property Relationships and Applications

et al. 2018

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Conjugated poly-ynes and poly(metalla-ynes) constitute an important class of new materials with potential application in various domains of science. The key factors responsible for the diverse usage of these materials is their intriguing and tunable chemical and photophysical properties. This review highlights fascinating advances made in the field of conjugated organic poly-ynes and poly(metalla-ynes) incorporating group 4-11 metals. This includes several important aspects of conjugated poly-ynes viz. synthetic protocols, bonding, electronic structure, nature of luminescence, structure-property relationships, diverse applications, and concluding remarks. Furthermore, we delineated the future directions and challenges in this particular area of research.

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“…L1 is emissive at 298 and 77 K in the solid state and in solution (Figure and Table ). The emission signature is reminiscent of what is commonly observed for Pt(II) species bearing CCAr moieties (Ar = aromatic) . The emission lifetimes (τ e ) are in the microsecond time scale, which are indicative of a triplet state emission.…”

Section: Resultsmentioning

confidence: 99%

“…The emission signature is reminiscent of what is commonly observed for Pt(II) species bearing CCAr moieties (Ar = aromatic). 40 The emission lifetimes (τ e ) are in the microsecond time scale, which are indicative of a triplet state emission. The presence of multiple components in the emission decays for both solution (sol.)…”

Section: ■ Results and Discussionmentioning

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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Organometallic and Coordination Polymers, and Linear and Star Oligomers Using the trans-Pt(PR3)2(C≡C)2 Linker

Cited by 13 publications

References 93 publications

A Fused Poly(truncated rhombic dodecahedron)-Containing 3D Coordination Polymer: A Multifunctional Material with Exceptional Properties

A Fused Poly(truncated rhombic dodecahedron)-Containing 3D Coordination Polymer: A Multifunctional Material with Exceptional Properties

Rise of Conjugated Poly-ynes and Poly(Metalla-ynes): From Design Through Synthesis to Structure–Property Relationships and Applications

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

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