“…The IR shift is usually considered to be a direct evidence for surface modification [11,12]. The IR spectrum of [NiTTO] n exhibits two bands at about 1168 and 1113 cm À1 , which can be ascribed to the C ¼ S stretching modes.…”
Section: Nanocrystalsmentioning
confidence: 99%
“…TTO (tetrathiooxalate, C 2 S 2À 4 ) serves as a bridge ligand to prepare metal complexes used for molecular conductors or magnetic materials [13][14][15]. Nickel tetrathiooxalates [Ni (TTO)] n is known as organic-inorganic hybrid oligomer with high electrical conductivity and strong absorption over a broad infrared range [11,12,[16][17][18]. We are interest in metal compounds and clusters assembled with those dithiolate molecules [19][20][21].…”
mentioning
confidence: 99%
“…Over the past decades, organic sulfur-rich compounds, such as dithiolate and tetrathiafulvalene, are attracted widely attention for their unique electronic, magnetic and optical properties [6][7][8][9][10]. Recently, Tieke et al [11,12] have reported the [Ni (TTO)] modification on bulky substrates and measured the conductivity. TTO (tetrathiooxalate, C 2 S 2À 4 ) serves as a bridge ligand to prepare metal complexes used for molecular conductors or magnetic materials [13][14][15].…”
“…The IR shift is usually considered to be a direct evidence for surface modification [11,12]. The IR spectrum of [NiTTO] n exhibits two bands at about 1168 and 1113 cm À1 , which can be ascribed to the C ¼ S stretching modes.…”
Section: Nanocrystalsmentioning
confidence: 99%
“…TTO (tetrathiooxalate, C 2 S 2À 4 ) serves as a bridge ligand to prepare metal complexes used for molecular conductors or magnetic materials [13][14][15]. Nickel tetrathiooxalates [Ni (TTO)] n is known as organic-inorganic hybrid oligomer with high electrical conductivity and strong absorption over a broad infrared range [11,12,[16][17][18]. We are interest in metal compounds and clusters assembled with those dithiolate molecules [19][20][21].…”
mentioning
confidence: 99%
“…Over the past decades, organic sulfur-rich compounds, such as dithiolate and tetrathiafulvalene, are attracted widely attention for their unique electronic, magnetic and optical properties [6][7][8][9][10]. Recently, Tieke et al [11,12] have reported the [Ni (TTO)] modification on bulky substrates and measured the conductivity. TTO (tetrathiooxalate, C 2 S 2À 4 ) serves as a bridge ligand to prepare metal complexes used for molecular conductors or magnetic materials [13][14][15].…”
“…Lbl assembly is based on electrostatic interaction between cationic and anionic species, , hydrogen bonding, − hydrophobic interaction, or coordinative bond formation between transition metal ions and organic ligands, with the latter also being called “reactive self-assembly”. − Reactive self-assembly is especially attractive for the preparation of ultrathin films of supramolecular coordination polymers. Recent examples comprise new ultrathin films of zinc-bisquinoline, zirconium-tetrasalicylidene-diaminobenzidine, metal tetrathiooxalates, , and others, − which exhibit interesting photo- and electroactive properties. − A general reaction scheme describing the reactive self-assembly of bis-bidentate ligands and divalent metal ions under the formation of coordination polymer films is outlined in Figure . 1 General scheme of the reactive self-assembly of divalent metal ions and bis-bidentate ligand molecules.…”
New metal-Schiff-base coordination polymer films were prepared using multiple sequential adsorption of metal ions and salen-based ligand molecules. As the ligands, bis-bidentate 5,5'-methylene-bis(N-methylsalicylidenamine) (MBSA), tetra-bidentate N,N',N' ',N' ''-tetrasalicylidene-polyamidoamine (TSPA), and multi-bidentate poly(N-salicylidenevinylamine) (PSVA) were used. The metal ions were Cu(II), Zn(II), Fe(II), Fe(III), and Ce(IV). The resulting films are deeply colored due to the formation of coordinative bonds between the metal ions and the salen groups. Our study indicates that film formation becomes progressively easier, if the number of salen groups per ligand molecule increases. While Cu(II), Ni(II), Fe, and Ce(IV) are well suited for complex formation, Zn(II) is less suited. Possible structures of the polymers are discussed. Cyclic voltammetric studies of the films are also presented.
Organic and inorganic materials with redox-controllable coloration and two or more stable valence states are of interest for applications in electrochromic and sensing devices. [1][2][3] Commercial applications require materials with film-forming properties, high stability, high contrast, and switching speed. Film formation can be achieved via spin-coating, solvent evaporation, electrochemical deposition, or layer-by-layer assembly.[4] The latter method is advantageous because it can be used to assemble ultrathin films of a variety of organic and inorganic compounds in a simple and inexpensive manner, with thickness control in the nanometer range.Previous work on preparation of electrochromic layer-by-layer assemblies was based on the use of polymers containing redoxactive viologen [5,6] or triphenylamine units, [7] conjugated polyelectrolytes, such as polythiophene derivatives [8][9][10] and polyaniline (PANI), [11] or colloidal solutions of Prussian Blue nanoparticles. [11,12] In most cases, film formation was brought about by alternating electrostatic assembly of electroactive components and nonactive counter-polyelectrolytes, utilizing the layer-by-layer technique first reported by Decher and coworkers. [13] Our contribution differs from the previous ones in that a crosslinked organic-inorganic coordination polymer is built up stepwise on a solid support, and no counter-polyelectrolyte is needed. The preparation method is similar to Decher's technique, in that the substrate is alternately dipped into two different solutions causing the sequential buildup of the polymer film at the substrate surface. However, in our case the two solutions contain a) a metal salt, such as zinc hexafluorophosphate, and b) a polymeric polytopic ligand, such as P1-2, which is composed of a polyiminofluorene backbone [14] with phenylterpyridine substituent groups attached to the nitrogen atom of the backbone. Synthesis and molecular structure are shown in Scheme 1a, and the self-assembly process is depicted in Scheme 2. The terpyridine (tpy) groups are capable of forming metal complexes of D 2d -symmetry with divalent zinc ions [15,16] (Scheme 1b). Due to the polytopic nature of the ligand P1-2, a network structure is formed, and the resulting coordination polymer is insoluble, so that it is easily immobilized at the substrate surface. Since the polytopic ligand is neutral, the buildup of the films proceeds exclusively via coordinative interactions. There is a similarity to the ''reactive self-assembly'' of previously reported films of coordination polymers, such as zinc bisquinoline, [17] metal tetrathiooxalates, [18] metal(IV)diphosphonates [19] metal hexacyanoferrates, [20] metal Schiff-base coordination polymers, [21] and others, [22,23] but in these cases the self-assembly is brought about by coordinative and electrostatic interactions simultaneously. There is also some analogy to functional metallo-supramolecular polyelectrolyte films and multilayers, reported by Kurth and coworkers.[24] However, in their work, first a line...
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