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).

Keywords

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

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@article{f9c8ac9d3c4d494b88f5573ba5f0ea24,

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.\}",

year = "2014",

month = apr,

day = "1",

doi = "10.1016/j.ica.2014.02.012",

language = "English",

volume = "414",

pages = "240--249",

journal = "Inorganica Chimica Acta",

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publisher = "Elsevier",

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TY - JOUR

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

Y1 - 2014/4/1

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

UR - https://www.scopus.com/pages/publications/84896540584

U2 - 10.1016/j.ica.2014.02.012

DO - 10.1016/j.ica.2014.02.012

M3 - Article

AN - SCOPUS:84896540584

SN - 0020-1693

VL - 414

SP - 240

EP - 249

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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