Silver(I) Bis(pyrazolyl)methane Complexes and Their Implementation as Precursors for Metallic Silver Deposition

Irene Bassanetti, Monica Mattarozzi, Massimiliano Delferro, Tobin J Marks, Luciano Marchiò

Research output: Contribution to journalArticle

4 Citations (Scopus)

Abstract

The following AgI bis(pyrazolyl)methane complexes with BF4 -/NO3 - as counteranions were synthesized and characterized: [Ag(LpzH)]2(NO3)2 (1), [Ag(LpzMe)]2(NO3)2 (2), [Ag(LpzH)]n(BF4)n (3), and [Ag(LpzMe)]n(BF4)n (4) [LpzH = bis(pyrazolyl)methane; LpzMe = bis(3,5-dimethylpyrazolyl)methane]. These complexes were prepared to identify optimum precursors for the thermolytic deposition of metallic silver. The crystal structures of 1 and 2 show that the complexes are dinuclear and that the NO3 - anions interact with the metals. In contrast, 3 is polymeric and the BF4 - does not interact with the metal. When crystallizing 1-4 in non-anhydrous solvents, the presence of adventitious water further reacts with 3 and 4 (but not with 1 and 2) to yield dinuclear complexes [Ag(LpzH)(H2O)2]2(BF4)2 (3a) and [Ag(LpzMe)(H2O)2]2(BF4)2 (4a). All of the dinuclear species 1, 2, 3a and 4a exhibit an argentophilic interaction with Ag···Ag distances in the range 3.18-2.99 Å. Thermogravimetric analysis (TGA) shows that 1 and 2 have lower decomposition temperatures (231 and 255 °C, respectively) than 3 and 4 (298 and 331 °C, respectively). 2 was further investigated as a precursor for metallic silver deposition by spin-coating solutions (10-3 M, THF/DMSO, 4:1), followed by annealing at 310 °C on 52100 steel substrates. According to energy-dispersive X-ray spectroscopy (EDS) and scanning electron microscopy (SEM) the metal deposition proceeds primarily via an island growth (Volmer-Weber) mechanism.

Original languageEnglish
JournalEuropean Journal of Inorganic Chemistry
DOIs
Publication statusAccepted/In press - 2015

Fingerprint

Methane
Silver
Metals
Steel
Spin coating
Dimethyl Sulfoxide
Anions
Thermogravimetric analysis
Energy dispersive spectroscopy
Crystal structure
Annealing
Decomposition
Scanning electron microscopy
Water
Substrates
Temperature

Keywords

  • Chemical vapor deposition
  • Metal deposition
  • N ligands
  • Silver

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

Silver(I) Bis(pyrazolyl)methane Complexes and Their Implementation as Precursors for Metallic Silver Deposition. / Bassanetti, Irene; Mattarozzi, Monica; Delferro, Massimiliano; Marks, Tobin J; Marchiò, Luciano.

In: European Journal of Inorganic Chemistry, 2015.

Research output: Contribution to journalArticle

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title = "Silver(I) Bis(pyrazolyl)methane Complexes and Their Implementation as Precursors for Metallic Silver Deposition",
abstract = "The following AgI bis(pyrazolyl)methane complexes with BF4 -/NO3 - as counteranions were synthesized and characterized: [Ag(LpzH)]2(NO3)2 (1), [Ag(LpzMe)]2(NO3)2 (2), [Ag(LpzH)]n(BF4)n (3), and [Ag(LpzMe)]n(BF4)n (4) [LpzH = bis(pyrazolyl)methane; LpzMe = bis(3,5-dimethylpyrazolyl)methane]. These complexes were prepared to identify optimum precursors for the thermolytic deposition of metallic silver. The crystal structures of 1 and 2 show that the complexes are dinuclear and that the NO3 - anions interact with the metals. In contrast, 3 is polymeric and the BF4 - does not interact with the metal. When crystallizing 1-4 in non-anhydrous solvents, the presence of adventitious water further reacts with 3 and 4 (but not with 1 and 2) to yield dinuclear complexes [Ag(LpzH)(H2O)2]2(BF4)2 (3a) and [Ag(LpzMe)(H2O)2]2(BF4)2 (4a). All of the dinuclear species 1, 2, 3a and 4a exhibit an argentophilic interaction with Ag···Ag distances in the range 3.18-2.99 {\AA}. Thermogravimetric analysis (TGA) shows that 1 and 2 have lower decomposition temperatures (231 and 255 °C, respectively) than 3 and 4 (298 and 331 °C, respectively). 2 was further investigated as a precursor for metallic silver deposition by spin-coating solutions (10-3 M, THF/DMSO, 4:1), followed by annealing at 310 °C on 52100 steel substrates. According to energy-dispersive X-ray spectroscopy (EDS) and scanning electron microscopy (SEM) the metal deposition proceeds primarily via an island growth (Volmer-Weber) mechanism.",
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AU - Bassanetti, Irene

AU - Mattarozzi, Monica

AU - Delferro, Massimiliano

AU - Marks, Tobin J

AU - Marchiò, Luciano

PY - 2015

Y1 - 2015

N2 - The following AgI bis(pyrazolyl)methane complexes with BF4 -/NO3 - as counteranions were synthesized and characterized: [Ag(LpzH)]2(NO3)2 (1), [Ag(LpzMe)]2(NO3)2 (2), [Ag(LpzH)]n(BF4)n (3), and [Ag(LpzMe)]n(BF4)n (4) [LpzH = bis(pyrazolyl)methane; LpzMe = bis(3,5-dimethylpyrazolyl)methane]. These complexes were prepared to identify optimum precursors for the thermolytic deposition of metallic silver. The crystal structures of 1 and 2 show that the complexes are dinuclear and that the NO3 - anions interact with the metals. In contrast, 3 is polymeric and the BF4 - does not interact with the metal. When crystallizing 1-4 in non-anhydrous solvents, the presence of adventitious water further reacts with 3 and 4 (but not with 1 and 2) to yield dinuclear complexes [Ag(LpzH)(H2O)2]2(BF4)2 (3a) and [Ag(LpzMe)(H2O)2]2(BF4)2 (4a). All of the dinuclear species 1, 2, 3a and 4a exhibit an argentophilic interaction with Ag···Ag distances in the range 3.18-2.99 Å. Thermogravimetric analysis (TGA) shows that 1 and 2 have lower decomposition temperatures (231 and 255 °C, respectively) than 3 and 4 (298 and 331 °C, respectively). 2 was further investigated as a precursor for metallic silver deposition by spin-coating solutions (10-3 M, THF/DMSO, 4:1), followed by annealing at 310 °C on 52100 steel substrates. According to energy-dispersive X-ray spectroscopy (EDS) and scanning electron microscopy (SEM) the metal deposition proceeds primarily via an island growth (Volmer-Weber) mechanism.

AB - The following AgI bis(pyrazolyl)methane complexes with BF4 -/NO3 - as counteranions were synthesized and characterized: [Ag(LpzH)]2(NO3)2 (1), [Ag(LpzMe)]2(NO3)2 (2), [Ag(LpzH)]n(BF4)n (3), and [Ag(LpzMe)]n(BF4)n (4) [LpzH = bis(pyrazolyl)methane; LpzMe = bis(3,5-dimethylpyrazolyl)methane]. These complexes were prepared to identify optimum precursors for the thermolytic deposition of metallic silver. The crystal structures of 1 and 2 show that the complexes are dinuclear and that the NO3 - anions interact with the metals. In contrast, 3 is polymeric and the BF4 - does not interact with the metal. When crystallizing 1-4 in non-anhydrous solvents, the presence of adventitious water further reacts with 3 and 4 (but not with 1 and 2) to yield dinuclear complexes [Ag(LpzH)(H2O)2]2(BF4)2 (3a) and [Ag(LpzMe)(H2O)2]2(BF4)2 (4a). All of the dinuclear species 1, 2, 3a and 4a exhibit an argentophilic interaction with Ag···Ag distances in the range 3.18-2.99 Å. Thermogravimetric analysis (TGA) shows that 1 and 2 have lower decomposition temperatures (231 and 255 °C, respectively) than 3 and 4 (298 and 331 °C, respectively). 2 was further investigated as a precursor for metallic silver deposition by spin-coating solutions (10-3 M, THF/DMSO, 4:1), followed by annealing at 310 °C on 52100 steel substrates. According to energy-dispersive X-ray spectroscopy (EDS) and scanning electron microscopy (SEM) the metal deposition proceeds primarily via an island growth (Volmer-Weber) mechanism.

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