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

doi:10.1002/ejic.201501236

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

^*Corresponding author for this work

Chemistry

Research output: Contribution to journal › Article › peer-review

10 Scopus citations

Abstract

The following Ag^Ibis(pyrazolyl)methane complexes with BF₄^–/NO₃^–as counteranions were synthesized and characterized: [Ag(L^pzH)]₂(NO₃)₂(1), [Ag(L^pzMe)]₂(NO₃)₂(2), [Ag(L^pzH)]_n(BF₄)_n(3), and [Ag(L^pzMe)]_n(BF₄)_n(4) [L^pzH= bis(pyrazolyl)methane; L^pzMe= 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(L^pzH)(H₂O)₂]₂(BF₄)₂(3a) and [Ag(L^pzMe)(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^–3m, 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 language	English (US)
Pages (from-to)	2626-2633
Number of pages	8
Journal	European Journal of Inorganic Chemistry
Volume	2016
Issue number	15-16
DOIs	https://doi.org/10.1002/ejic.201501236
State	Published - Jun 2016

Funding

Financial support from the University of Parma is acknowledged. Research at Northwestern was made possible by National Priorities Research Program (NPRP) (grant number 5-192-1-046) from the Qatar National Research Fund (a member of the Qatar Foundation) The statements made herein are solely the responsibility of the author(s). We thank the NSF-MRSEC program through the Northwestern University Materials Research Science and Engineering Center for characterization facilities (DMR-1121262), and NSF Chemistry Division (CHE-1048773) for supporting the purchases of the NMR instrumentation at IMSERC. I. B. thanks the University of Parma (Italy) for a study leave.

Keywords

Chemical vapor deposition
Metal deposition
N ligands
Silver

ASJC Scopus subject areas

Inorganic Chemistry

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10.1002/ejic.201501236

Cite this

@article{436bfd5fd7e344519be51270a6e6594d,

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

abstract = "The following AgIbis(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 (10–3m, 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.",

keywords = "Chemical vapor deposition, Metal deposition, N ligands, Silver",

author = "Irene Bassanetti and Monica Mattarozzi and Massimiliano Delferro and Marks, {Tobin J.} and Luciano Marchi{\`o}",

note = "Funding Information: Financial support from the University of Parma is acknowledged. Research at Northwestern was made possible by National Priorities Research Program (NPRP) (grant number 5-192-1-046) from the Qatar National Research Fund (a member of the Qatar Foundation) The statements made herein are solely the responsibility of the author(s). We thank the NSF-MRSEC program through the Northwestern University Materials Research Science and Engineering Center for characterization facilities (DMR-1121262), and NSF Chemistry Division (CHE-1048773) for supporting the purchases of the NMR instrumentation at IMSERC. I. B. thanks the University of Parma (Italy) for a study leave. Publisher Copyright: {\textcopyright} 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.",

year = "2016",

month = jun,

doi = "10.1002/ejic.201501236",

language = "English (US)",

volume = "2016",

pages = "2626--2633",

journal = "European Journal of Inorganic Chemistry",

issn = "1434-1948",

publisher = "Wiley-VCH Verlag",

number = "15-16",

}

TY - JOUR

T1 - Silver(I) Bis(pyrazolyl)methane Complexes and Their Implementation as Precursors for Metallic Silver Deposition

AU - Bassanetti, Irene

AU - Mattarozzi, Monica

AU - Delferro, Massimiliano

AU - Marks, Tobin J.

AU - Marchiò, Luciano

N1 - Funding Information: Financial support from the University of Parma is acknowledged. Research at Northwestern was made possible by National Priorities Research Program (NPRP) (grant number 5-192-1-046) from the Qatar National Research Fund (a member of the Qatar Foundation) The statements made herein are solely the responsibility of the author(s). We thank the NSF-MRSEC program through the Northwestern University Materials Research Science and Engineering Center for characterization facilities (DMR-1121262), and NSF Chemistry Division (CHE-1048773) for supporting the purchases of the NMR instrumentation at IMSERC. I. B. thanks the University of Parma (Italy) for a study leave. Publisher Copyright: © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

PY - 2016/6

Y1 - 2016/6

N2 - The following AgIbis(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 (10–3m, 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 AgIbis(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 (10–3m, 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.

KW - Chemical vapor deposition

KW - Metal deposition

KW - N ligands

KW - Silver

UR - http://www.scopus.com/inward/record.url?scp=84950000515&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84950000515&partnerID=8YFLogxK

U2 - 10.1002/ejic.201501236

DO - 10.1002/ejic.201501236

M3 - Article

AN - SCOPUS:84950000515

SN - 1434-1948

VL - 2016

SP - 2626

EP - 2633

JO - European Journal of Inorganic Chemistry

JF - European Journal of Inorganic Chemistry

IS - 15-16

ER -

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

Abstract

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ASJC Scopus subject areas

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CCDC 1421548: Experimental Crystal Structure Determination

CCDC 1421550: Experimental Crystal Structure Determination

CCDC 1421549: Experimental Crystal Structure Determination

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

Abstract

Funding

Keywords

ASJC Scopus subject areas

Access to Document

Other files and links

Fingerprint

Datasets

CCDC 1421548: Experimental Crystal Structure Determination

CCDC 1421550: Experimental Crystal Structure Determination

CCDC 1421549: Experimental Crystal Structure Determination

Cite this