Self‐assembly of π‐conjugated bis(terpyridine) ligands with zinc(II) ions: New metallosupramolecular materials for optoelectronic applications

Winter, Andreas; Friebe, Christian; Chiper, Manuela; Hager, Martin D.; Schubert, Ulrich S.

doi:10.1002/pola.23469

Cited by 83 publications

(93 citation statements)

References 94 publications

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“…In addition, a ruthenium complex incorporated into a polymer will influence the optical as well as the electronic properties of the polymer due to its characteristic metal-to-ligand charge transfer (MLCT) transition around 500 nm, thus extending the absorption range of the material. The usage of Zn II ions leads to metallo-polymers being potential interesting light-emitting materials in OLEDs; [14,15,[21][22][23] moreover, also Ir-containing polymers are of special interest for this purpose. [24][25][26] In recent years, p-conjugated polymer semiconductors with donor-acceptor (D-A) architectures have attracted considerable attention, since their electro-optical properties make them promising candidates for potential applications in the fields of organic electronics.…”

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confidence: 99%

π‐Conjugated Donor and Donor–Acceptor Metallo‐Polymers

Wild

Schlütter

Pavlov

et al. 2010

Macromol. Rapid Commun.

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Two zinc(II)‐ and two ruthenium(II) containing π‐conjugated metallo‐polymers were synthesized and characterized in detail. We could prove by SEC, analytical ultracentrifugation (AUC) and viscosimetry the ruthenium(II) metallo‐polymers to be high molar mass materials (Mfs = 20 000 g · mol−1 Ru1‐2; Mfs = 34 000 g · mol−1 Ru1) exhibiting intrinsic viscosities of up to [η] = 192 · cm3 · g−1. Applying spin‐coating we produced homogeneous films of the polymers and could, subsequently, investigate the photophysical properties in the solid state. Introducing the Ru(II) metallo‐polymers mixed with PCBM[60] as photoactive layer in bulk‐heterojunction solar cells resulted in very low efficiencies due to morphology problems. magnified image

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confidence: 99%

π‐Conjugated Donor and Donor–Acceptor Metallo‐Polymers

Wild

Schlütter

Pavlov

et al. 2010

Macromol. Rapid Commun.

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“…This allows the synthesis of materials that show tailor-made optical properties. As a continuation of previous work in the field of π-conjugated terpyridines and their applications in supramolecular chemistry, [27][28][29] in which we synthesized systems with different geometries [30,31] and introduced the Huisgen reaction to the field of conjugated terpyridines, [32] we have studied the effect of the systematic variation of both the spacer unit and the linker in conjugated bis(terpyridines). This should allow the elucidation of selected structure-property relationships of these materials.…”

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confidence: 99%

π‐Conjugated 2,2′:6′,2″‐Bis(terpyridines): Systematical Tuning of the Optical Properties by Variation of the Linkage between the Terpyridines and the π‐Conjugated System

et al. 2010

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Abstract2,2′:6′,2″‐Terpyridines bearing well‐defined π‐conjugated substituents at the 4′‐position are known to exhibit interesting electronic and optical properties. The systematic variation of both the spacer unit and the linker in conjugated bis(terpyridines) has resulted in a library of π‐conjugated systems, enabling the study of the structure–property relationships of these materials. We have proven the Huisgen 1,3‐dipolar cycloaddition reaction to be a versatile tool for connecting conjugated systems, even though the conjugation is hindered by the introduced triazole moiety. All the terpyridine derivatives were fully characterized by 1H and 13C NMR spectroscopy, UV/Vis absorption and emission measurements as well as MALDI‐TOF MS. Thin films of the materials were produced by spin‐coating and subsequently characterized. Because tuning of the band gap of the materials over a wide range is possible, quantum yields of up to 85 % and extinction coefficients of around 100000 M–1 cm–1 could be observed, the compounds might be promising candidates for the design of new functional supramolecular materials.

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“…By varying the grafting concentration the PL performances were preserved or enhanced with respect to the low molecular weight complexes. Some PLQY values resulted unprecedented among analogous metallopolymer systems, [25][26][27] as it will be discussed.…”

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confidence: 99%

High Solid State Photoluminescence Quantum Yields and Effective Color Tuning in Polyvinylpyridine Based Zinc(II) Metallopolymers

Borbone

Caruso

Palma

et al. 2015

Macro Chemistry & Physics

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Two series of amorphous metallopolymers are produced by grafting N′-substituted aroylhydrazide zinc(II) coordinated fragments onto poly-(4-vinylpyridine) at several concentrations. The polymers are characterized concerning their thermal behavior and absorption/emission properties. In the solid state their photoluminescence (PL) performances are remarkable. The emission color can be effectively tuned across the entire visible spectrum by varying the strength of the electron acceptor substituent on the tridentate ligand. As concerns the emission intensity, PL quantum yields measured on spin coated thin fi lms range from medium to high values and greatly exceed those of the model molecular complexes. Some of these values can be considered among the highest reported in the literature for metallopolymers. through chemical synthesis. [1][2][3][4][5][6][7][8] Among these materials polymers containing transition metal complexes (metallopolymers) are an important class whose electron rich ligands and metal centers can enhance optical and electronic properties. [9][10][11][12][13] In the last years our research group focused interest [14][15][16] on O,N ligands with functional substituents able to coordinate a d 10 transition metal ion like Zn(II) into stable chelate complexes with interesting photoluminescence performances. [ 17 ] In a recent study [ 15,16 ] N′-substituted aroylhydrazide fragments acted as O,N,O tridentate ligands in mono and dinuclear Zn(II) complexes with high photoluminescence quantum yield (PLQY) in the solid state. The ability of pyridine molecules to complete the coordination sphere of the complexes in penta or hexacoordinated arrangements was explored and its dominant contribution to the lowest unoccupied molecular orbital (LUMO) involved in the electronic transitions was pointed up. The present work has the purpose

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Self‐assembly of π‐conjugated bis(terpyridine) ligands with zinc(II) ions: New metallosupramolecular materials for optoelectronic applications

Cited by 83 publications

References 94 publications

π‐Conjugated Donor and Donor–Acceptor Metallo‐Polymers

π‐Conjugated Donor and Donor–Acceptor Metallo‐Polymers

π‐Conjugated 2,2′:6′,2″‐Bis(terpyridines): Systematical Tuning of the Optical Properties by Variation of the Linkage between the Terpyridines and the π‐Conjugated System

High Solid State Photoluminescence Quantum Yields and Effective Color Tuning in Polyvinylpyridine Based Zinc(II) Metallopolymers

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