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

Keywords

Chemical vapor deposition
Metal deposition
N ligands
Silver

ASJC Scopus subject areas

Inorganic Chemistry

Access to Document

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 = "Berichte der deutschen chemischen Gesellschaft",

issn = "0365-9496",

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

VL - 2016

SP - 2626

EP - 2633

JO - Berichte der deutschen chemischen Gesellschaft

JF - Berichte der deutschen chemischen Gesellschaft

SN - 0365-9496

IS - 15-16

ER -

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

Abstract

Keywords

ASJC Scopus subject areas

Access to Document

Other files and links

Fingerprint

CCDC 1421550: Experimental Crystal Structure Determination

CCDC 1421552: Experimental Crystal Structure Determination

CCDC 1421548: Experimental Crystal Structure Determination

Cite this

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

Abstract

Keywords

ASJC Scopus subject areas

Access to Document

Other files and links

Fingerprint

Datasets

CCDC 1421550: Experimental Crystal Structure Determination

CCDC 1421552: Experimental Crystal Structure Determination

CCDC 1421548: Experimental Crystal Structure Determination

Cite this