Guanidine Electron Donors and Silver Halides: Interplay and Competition between Redox, Coordination and Polymerization Reactions

Emeljanenko, Dimitri; Horn, Julian; Kaifer, Elisabeth; Wadepohl, Hubert; Himmel, Hans‐Jörg

doi:10.1002/ejic.201101002

Cited by 12 publications

(3 citation statements)

References 26 publications

(38 reference statements)

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“…Hence the experiments with model compounds 3 and 4 motivate the synthesis of chain polymers in which the guanidine building blocks are connected by single cobalt ions. However, reaction between the known dinuclear complex [( 1 )(CoCl 2 ) 2 ]16 and AgPF 6 yielded not the desired 1D polymer {[( 1 )Co](PF 6 ) 4 } n , but polymer {( 1 )Ag 4 Cl 6 } n (also 1D), in which cobalt is replaced by silver 36. Therefore, alternative routes have to be applied.…”

Section: Resultssupporting

confidence: 81%

Highly Oxidized Semiconducting Coordination Polymers – Coupled Oxidation and Coordination of Guanidine Electron Donors

et al. 2012

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Redox and coordination processes are coupled in the course of reactions of the organic electron donors 1,2,4,5‐tetrakis(tetramethylguanidino)benzene (1) and 1,2,4,5‐tetrakis(N,N′‐dimethyl‐N,N′‐ethyleneguanidino)benzene (2) with silver salts. Experiments with several different silver salts show that the product structure is significantly affected by the properties of the anion in these salts. Chain polymers are the products of reactions with AgPF6 or AgBF4, in which dicationic organic building blocks are connected by silver ions. Experiments with AgNO3 yielded either dinuclear complexes (with 1) or 2D networks (with 2). If the salt Ag[Al{OC(CF3)3}4], featuring a weakly coordinating anion, was used, simple silver‐free salts of the guanidine dication were obtained. The thermal stability, optical properties, and electrical conductivity were studied in detail for the product polymer {[(1)Ag](PF6)3}n. From the temperature dependence of the electric conductivity, this compound was found to be a semiconductor with a band gap of approximately 3 eV. The experiments were complemented by quantum chemical calculations at density‐functional‐theory level on the band structure of this and a related polymer. The electronic situation was further analyzed with the aid of molecular model complexes, which were either synthesized or calculated.

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Section: Resultssupporting

confidence: 81%

Highly Oxidized Semiconducting Coordination Polymers – Coupled Oxidation and Coordination of Guanidine Electron Donors

et al. 2012

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“…For example, all dinuclear Cu I and Ag I complexes characterized so far feature threefold coordinated metal ions. Figure 10 shows the complexes [ttmgb(Ag X ) 2 ] (with X = Cl50 or CN), which are both of the general type [Ag I | GFA | Ag I ]. The low coordination number should allow oxidative addition reactions to occur.…”

Section: Molecular Late‐transition Metal Complexesmentioning

confidence: 99%

Guanidinyl‐Functionalized Aromatic Compounds (GFAs) – Charge and Spin Density Studies as Starting Points for the Development of a New Class of Redox‐active Ligands

Himmel

2013

Zeitschrift anorg allge chemie

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“…Reactions between ttmgb and some silver compounds have been studied previously. In the case of silver halides, coordination competes with redox reactions and the chosen reaction channel was shown to be extremely sensitive to the reaction conditions, especially solvent polarity 16. Reactions between guanidine electron donors and the silver salts of weakly coordinating anions led to coordination polymers;17,18 the 1D polymers {[Ag(ttmgb)](PF 6 ) 3 } n and {[Ag(ttmgb)](BF 4 ) 3 } n were obtained as products of reactions between ttmgb and AgPF 6 or AgBF 4 , respectively 17.…”

Section: Introductionmentioning

confidence: 99%

Redox Reactions Between Guanidine Electron Donors and Silver Dicyanamide: Synthesis of C,N Material Precursors and Coordination Polymers

et al. 2013

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Reaction of the organic electron donors ttmgb [1,2,4,5‐tetrakis(tetramethylguanidinyl)benzene] and tdmegb [1,2,4,5‐tetrakis(N,N′‐dimethylethyleneguanidinyl)benzene] with two equivalents of silver dicyanamide, Ag(dca), yielded the two salts (ttmgb)(dca)2 (1a) and (tdmegb)(dca)2 (1b). Their relatively high N/C ratios motivated an analysis of their suitability as precursors to C,N materials. The compounds melt at around 200 °C and decompose at 220 (1a) and 245 °C (1b). Reactions of the organic electron donors with an excess of Ag(dca) resulted in coupled redox and coordination reactions, leading finally to coordination polymers with different dimensionalities. The oxidized guanidine units in the polymers are connected through Ag–dca–Ag bridges, leading to stacks of co‐planar C6 rings. The resulting cationic networks are neutralized by dca anions or anionic Ag(dca) chains.

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Guanidine Electron Donors and Silver Halides: Interplay and Competition between Redox, Coordination and Polymerization Reactions

Cited by 12 publications

References 26 publications

Highly Oxidized Semiconducting Coordination Polymers – Coupled Oxidation and Coordination of Guanidine Electron Donors

Highly Oxidized Semiconducting Coordination Polymers – Coupled Oxidation and Coordination of Guanidine Electron Donors

Guanidinyl‐Functionalized Aromatic Compounds (GFAs) – Charge and Spin Density Studies as Starting Points for the Development of a New Class of Redox‐active Ligands

Redox Reactions Between Guanidine Electron Donors and Silver Dicyanamide: Synthesis of C,N Material Precursors and Coordination Polymers

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