Synthesis, structures, and photoluminescence properties of lanthanide dicyanoaurates containing dimeric aurophilic interactions

Frankie White; Lam N. Pham; Kang Rui Xiang; Rylee Thomas; Paul Vogel; Carlos Crawford; Zerihun Assefa; Richard E. Sykora

doi:10.1016/j.ica.2014.02.012

Synthesis, structures, and photoluminescence properties of lanthanide dicyanoaurates containing dimeric aurophilic interactions

Frankie White, Lam N. Pham, Kang Rui Xiang, Rylee Thomas, Paul Vogel, Carlos Crawford, Zerihun Assefa, Richard E. Sykora

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

10 Scopus citations

Abstract

The synthesis of a series of lanthanide dicyanoaurates containing the ancillary ligand 2,2′:6′,2″-terpyridine (terpy) have been carried out by reaction of Ln³⁺ nitrate salts with terpy and potassium dicyanoaurate. The resultant compounds, [Ln(C₁₅H ₁₁N₃)(H₂O)(NO₃)₂Au(CN) ₂] (Ln = Eu, Tb, Dy, Ho, Er, Yb), form an isostructural series as established by single-crystal X-ray diffraction studies. These studies reveal the existence of two important non-covalent interactions in these compounds. Dimeric aurophilic interactions and terpyridine π-stacking are both present with distances of ∼3.5 Å for each. Photoluminescence measurements illustrate that the Eu³⁺ and Tb³⁺ compounds display enhanced Ln-based emission due to intramolecular energy transfer from the coordinated terpy ligands. Additionally, a [Au(CN)₂^-] ₂ dimeric excimer produces a broad, green emission band in this class of compounds, albeit reduced in intensity in several of the compounds where a reasonable energy match exists with Ln³⁺ excitation bands.

Original language	English
Pages (from-to)	240-249
Number of pages	10
Journal	Inorganica Chimica Acta
Volume	414
DOIs	https://doi.org/10.1016/j.ica.2014.02.012
State	Published - Apr 1 2014
Externally published	Yes

Funding

The authors gratefully acknowledge the National Science Foundation for their generous support ( NSF -CAREER grant to R.E.S., CHE-0846680 ). Z.A also gratefully acknowledges NSF support ( CHE-0959406 ) and the NOAA Educational Partnership Program award number NA06OAR4810187 to NCAT State University as well as support from the donors of the Petroleum Research Fund (ACS-PRF).

Funders	Funder number
ACS-PRF
National Science Foundation	CHE-0846680, CHE-0959406
National Oceanic and Atmospheric Administration	NA06OAR4810187
American Chemical Society Petroleum Research Fund

Keywords

Dicyanoaurate
Energy transfer
Lanthanide
Photoluminescence
Single-crystal X-ray diffraction
Terpyridine

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10.1016/j.ica.2014.02.012

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title = "Synthesis, structures, and photoluminescence properties of lanthanide dicyanoaurates containing dimeric aurophilic interactions",

abstract = "The synthesis of a series of lanthanide dicyanoaurates containing the ancillary ligand 2,2′:6′,2″-terpyridine (terpy) have been carried out by reaction of Ln3+ nitrate salts with terpy and potassium dicyanoaurate. The resultant compounds, [Ln(C15H 11N3)(H2O)(NO3)2Au(CN) 2] (Ln = Eu, Tb, Dy, Ho, Er, Yb), form an isostructural series as established by single-crystal X-ray diffraction studies. These studies reveal the existence of two important non-covalent interactions in these compounds. Dimeric aurophilic interactions and terpyridine π-stacking are both present with distances of ∼3.5 {\AA} for each. Photoluminescence measurements illustrate that the Eu3+ and Tb3+ compounds display enhanced Ln-based emission due to intramolecular energy transfer from the coordinated terpy ligands. Additionally, a [Au(CN)2-] 2 dimeric excimer produces a broad, green emission band in this class of compounds, albeit reduced in intensity in several of the compounds where a reasonable energy match exists with Ln3+ excitation bands.",

keywords = "Dicyanoaurate, Energy transfer, Lanthanide, Photoluminescence, Single-crystal X-ray diffraction, Terpyridine",

author = "Frankie White and Pham, {Lam N.} and Xiang, {Kang Rui} and Rylee Thomas and Paul Vogel and Carlos Crawford and Zerihun Assefa and Sykora, {Richard E.}",

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T1 - Synthesis, structures, and photoluminescence properties of lanthanide dicyanoaurates containing dimeric aurophilic interactions

AU - White, Frankie

AU - Pham, Lam N.

AU - Xiang, Kang Rui

AU - Thomas, Rylee

AU - Vogel, Paul

AU - Crawford, Carlos

AU - Assefa, Zerihun

AU - Sykora, Richard E.

PY - 2014/4/1

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N2 - The synthesis of a series of lanthanide dicyanoaurates containing the ancillary ligand 2,2′:6′,2″-terpyridine (terpy) have been carried out by reaction of Ln3+ nitrate salts with terpy and potassium dicyanoaurate. The resultant compounds, [Ln(C15H 11N3)(H2O)(NO3)2Au(CN) 2] (Ln = Eu, Tb, Dy, Ho, Er, Yb), form an isostructural series as established by single-crystal X-ray diffraction studies. These studies reveal the existence of two important non-covalent interactions in these compounds. Dimeric aurophilic interactions and terpyridine π-stacking are both present with distances of ∼3.5 Å for each. Photoluminescence measurements illustrate that the Eu3+ and Tb3+ compounds display enhanced Ln-based emission due to intramolecular energy transfer from the coordinated terpy ligands. Additionally, a [Au(CN)2-] 2 dimeric excimer produces a broad, green emission band in this class of compounds, albeit reduced in intensity in several of the compounds where a reasonable energy match exists with Ln3+ excitation bands.

AB - The synthesis of a series of lanthanide dicyanoaurates containing the ancillary ligand 2,2′:6′,2″-terpyridine (terpy) have been carried out by reaction of Ln3+ nitrate salts with terpy and potassium dicyanoaurate. The resultant compounds, [Ln(C15H 11N3)(H2O)(NO3)2Au(CN) 2] (Ln = Eu, Tb, Dy, Ho, Er, Yb), form an isostructural series as established by single-crystal X-ray diffraction studies. These studies reveal the existence of two important non-covalent interactions in these compounds. Dimeric aurophilic interactions and terpyridine π-stacking are both present with distances of ∼3.5 Å for each. Photoluminescence measurements illustrate that the Eu3+ and Tb3+ compounds display enhanced Ln-based emission due to intramolecular energy transfer from the coordinated terpy ligands. Additionally, a [Au(CN)2-] 2 dimeric excimer produces a broad, green emission band in this class of compounds, albeit reduced in intensity in several of the compounds where a reasonable energy match exists with Ln3+ excitation bands.

KW - Dicyanoaurate

KW - Energy transfer

KW - Lanthanide

KW - Photoluminescence

KW - Single-crystal X-ray diffraction

KW - Terpyridine

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JO - Inorganica Chimica Acta

JF - Inorganica Chimica Acta

ER -

Synthesis, structures, and photoluminescence properties of lanthanide dicyanoaurates containing dimeric aurophilic interactions

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