Bismuth(iii)-thiophenedicarboxylates as host frameworks for lanthanide ions: Synthesis, structural characterization, and photoluminescent behavior

Alyssa K. Adcock; Bradley Gibbons; Jeffrey D. Einkauf; Jeffery A. Bertke; J. Faye Rubinson; Daniel T. De Lill; Karah E. Knope

doi:10.1039/c8dt02920b

Bismuth(iii)-thiophenedicarboxylates as host frameworks for lanthanide ions: Synthesis, structural characterization, and photoluminescent behavior

Alyssa K. Adcock, Bradley Gibbons, Jeffrey D. Einkauf, Jeffery A. Bertke, J. Faye Rubinson, Daniel T. De Lill, Karah E. Knope

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15 Scopus citations

Abstract

Three bismuth-2,5-thiophenedicarboxylates (Bi-TDC) and two europium-2,5-thiophenedicarboxylates (Eu-TDC) were synthesized under ambient conditions. The structures were determined through single crystal X-ray diffraction, and three of the phases were further characterized by powder X-ray diffraction, Raman spectroscopy, and thermogravimetric analysis. Reactions of bismuth nitrate, 2,5-thiophenedicarboxylate, and pyridine in an acidic solution of acetic acid and ethanol yield Hpy[Bi(TDC)₂(H₂O)]·1.5H₂O (1), whereas reactions in a water/ethanol mixture produce a minor phase, [Hpy]₃[Bi₂(TDC)₄(HTDC)(H₂O)]·xH₂O (2) along with a major product, (Hpy)₂[Bi(TDC)₂(HTDC)]·0.36H₂O (3). The structures of 1-3 are all built from anionic Bi-TDC chains that are further bridged through additional TDC linkages into interpenetrated 2D sheets. Addition of an aqueous lanthanide solution to the reaction mixtures that yielded 1 and 2-3 resulted in the formation of doped phases, Hpy[Bi_1-xLn_x(TDC)₂(H₂O)]·1.5H₂O (Bi_1-xLn_x-1), where Ln = Nd, Sm, Eu, Tb, Dy, and Yb, and (Hpy)₂[Bi_0.99Eu_0.01 (TDC)₂(HTDC)]·0.36H₂O (Bi_0.99Eu_0.01-3). Using europium nitrate rather than the bismuth precursor resulted in the formation of two homometallic europium based phases, [Eu(TDC)(NO₃)(H₂O)]_n (4) and [Eu₂(TDC)₃(H₂O)₉]·5H₂O (5), which adopt an extended 3D network and an interpenetrated 2D structure, respectively. Photophysical measurements were carried out for 1 and the lanthanide containing phases and quantum yield and lifetime values were determined for the visible light emitters. Herein, the structural chemistry, spectroscopic properties, and luminescence of the bismuth phases, their lanthanide doped analogs, and the europium compounds are presented.

Original language	English
Pages (from-to)	13419-13433
Number of pages	15
Journal	Dalton Transactions
Volume	47
Issue number	38
DOIs	https://doi.org/10.1039/c8dt02920b
State	Published - 2018
Externally published	Yes

Funding

The authors gratefully acknowledge the Clare Booth Luce Foundation for their support. The authors also acknowledge the National Science Foundation for acquisition of the single crystal X-ray diffractometer (NSF CHE-1337975) and the Raman spectrometer (NSF CHE-1429079), as well as funding for BG (NSF CHE-REU 1156788).

Funders	Funder number
National Science Foundation	CHE-1429079, CHE-REU 1156788, CHE-1337975

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10.1039/c8dt02920b

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@article{4566fe5fe40744fca0d7593ffbdfc9d8,

title = "Bismuth(iii)-thiophenedicarboxylates as host frameworks for lanthanide ions: Synthesis, structural characterization, and photoluminescent behavior",

abstract = "Three bismuth-2,5-thiophenedicarboxylates (Bi-TDC) and two europium-2,5-thiophenedicarboxylates (Eu-TDC) were synthesized under ambient conditions. The structures were determined through single crystal X-ray diffraction, and three of the phases were further characterized by powder X-ray diffraction, Raman spectroscopy, and thermogravimetric analysis. Reactions of bismuth nitrate, 2,5-thiophenedicarboxylate, and pyridine in an acidic solution of acetic acid and ethanol yield Hpy[Bi(TDC)2(H2O)]·1.5H2O (1), whereas reactions in a water/ethanol mixture produce a minor phase, [Hpy]3[Bi2(TDC)4(HTDC)(H2O)]·xH2O (2) along with a major product, (Hpy)2[Bi(TDC)2(HTDC)]·0.36H2O (3). The structures of 1-3 are all built from anionic Bi-TDC chains that are further bridged through additional TDC linkages into interpenetrated 2D sheets. Addition of an aqueous lanthanide solution to the reaction mixtures that yielded 1 and 2-3 resulted in the formation of doped phases, Hpy[Bi1-xLnx(TDC)2(H2O)]·1.5H2O (Bi1-xLnx-1), where Ln = Nd, Sm, Eu, Tb, Dy, and Yb, and (Hpy)2[Bi0.99Eu0.01 (TDC)2(HTDC)]·0.36H2O (Bi0.99Eu0.01-3). Using europium nitrate rather than the bismuth precursor resulted in the formation of two homometallic europium based phases, [Eu(TDC)(NO3)(H2O)]n (4) and [Eu2(TDC)3(H2O)9]·5H2O (5), which adopt an extended 3D network and an interpenetrated 2D structure, respectively. Photophysical measurements were carried out for 1 and the lanthanide containing phases and quantum yield and lifetime values were determined for the visible light emitters. Herein, the structural chemistry, spectroscopic properties, and luminescence of the bismuth phases, their lanthanide doped analogs, and the europium compounds are presented.",

author = "Adcock, {Alyssa K.} and Bradley Gibbons and Einkauf, {Jeffrey D.} and Bertke, {Jeffery A.} and Rubinson, {J. Faye} and {De Lill}, {Daniel T.} and Knope, {Karah E.}",

note = "Publisher Copyright: {\textcopyright} 2018 The Royal Society of Chemistry.",

year = "2018",

doi = "10.1039/c8dt02920b",

language = "English",

volume = "47",

pages = "13419--13433",

journal = "Dalton Transactions",

issn = "1477-9226",

publisher = "Royal Society of Chemistry",

number = "38",

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TY - JOUR

T1 - Bismuth(iii)-thiophenedicarboxylates as host frameworks for lanthanide ions

T2 - Synthesis, structural characterization, and photoluminescent behavior

AU - Adcock, Alyssa K.

AU - Gibbons, Bradley

AU - Einkauf, Jeffrey D.

AU - Bertke, Jeffery A.

AU - Rubinson, J. Faye

AU - De Lill, Daniel T.

AU - Knope, Karah E.

PY - 2018

Y1 - 2018

N2 - Three bismuth-2,5-thiophenedicarboxylates (Bi-TDC) and two europium-2,5-thiophenedicarboxylates (Eu-TDC) were synthesized under ambient conditions. The structures were determined through single crystal X-ray diffraction, and three of the phases were further characterized by powder X-ray diffraction, Raman spectroscopy, and thermogravimetric analysis. Reactions of bismuth nitrate, 2,5-thiophenedicarboxylate, and pyridine in an acidic solution of acetic acid and ethanol yield Hpy[Bi(TDC)2(H2O)]·1.5H2O (1), whereas reactions in a water/ethanol mixture produce a minor phase, [Hpy]3[Bi2(TDC)4(HTDC)(H2O)]·xH2O (2) along with a major product, (Hpy)2[Bi(TDC)2(HTDC)]·0.36H2O (3). The structures of 1-3 are all built from anionic Bi-TDC chains that are further bridged through additional TDC linkages into interpenetrated 2D sheets. Addition of an aqueous lanthanide solution to the reaction mixtures that yielded 1 and 2-3 resulted in the formation of doped phases, Hpy[Bi1-xLnx(TDC)2(H2O)]·1.5H2O (Bi1-xLnx-1), where Ln = Nd, Sm, Eu, Tb, Dy, and Yb, and (Hpy)2[Bi0.99Eu0.01 (TDC)2(HTDC)]·0.36H2O (Bi0.99Eu0.01-3). Using europium nitrate rather than the bismuth precursor resulted in the formation of two homometallic europium based phases, [Eu(TDC)(NO3)(H2O)]n (4) and [Eu2(TDC)3(H2O)9]·5H2O (5), which adopt an extended 3D network and an interpenetrated 2D structure, respectively. Photophysical measurements were carried out for 1 and the lanthanide containing phases and quantum yield and lifetime values were determined for the visible light emitters. Herein, the structural chemistry, spectroscopic properties, and luminescence of the bismuth phases, their lanthanide doped analogs, and the europium compounds are presented.

AB - Three bismuth-2,5-thiophenedicarboxylates (Bi-TDC) and two europium-2,5-thiophenedicarboxylates (Eu-TDC) were synthesized under ambient conditions. The structures were determined through single crystal X-ray diffraction, and three of the phases were further characterized by powder X-ray diffraction, Raman spectroscopy, and thermogravimetric analysis. Reactions of bismuth nitrate, 2,5-thiophenedicarboxylate, and pyridine in an acidic solution of acetic acid and ethanol yield Hpy[Bi(TDC)2(H2O)]·1.5H2O (1), whereas reactions in a water/ethanol mixture produce a minor phase, [Hpy]3[Bi2(TDC)4(HTDC)(H2O)]·xH2O (2) along with a major product, (Hpy)2[Bi(TDC)2(HTDC)]·0.36H2O (3). The structures of 1-3 are all built from anionic Bi-TDC chains that are further bridged through additional TDC linkages into interpenetrated 2D sheets. Addition of an aqueous lanthanide solution to the reaction mixtures that yielded 1 and 2-3 resulted in the formation of doped phases, Hpy[Bi1-xLnx(TDC)2(H2O)]·1.5H2O (Bi1-xLnx-1), where Ln = Nd, Sm, Eu, Tb, Dy, and Yb, and (Hpy)2[Bi0.99Eu0.01 (TDC)2(HTDC)]·0.36H2O (Bi0.99Eu0.01-3). Using europium nitrate rather than the bismuth precursor resulted in the formation of two homometallic europium based phases, [Eu(TDC)(NO3)(H2O)]n (4) and [Eu2(TDC)3(H2O)9]·5H2O (5), which adopt an extended 3D network and an interpenetrated 2D structure, respectively. Photophysical measurements were carried out for 1 and the lanthanide containing phases and quantum yield and lifetime values were determined for the visible light emitters. Herein, the structural chemistry, spectroscopic properties, and luminescence of the bismuth phases, their lanthanide doped analogs, and the europium compounds are presented.

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U2 - 10.1039/c8dt02920b

DO - 10.1039/c8dt02920b

M3 - Article

C2 - 30183020

AN - SCOPUS:85054060459

SN - 1477-9226

VL - 47

SP - 13419

EP - 13433

JO - Dalton Transactions

JF - Dalton Transactions

IS - 38

ER -

Bismuth(iii)-thiophenedicarboxylates as host frameworks for lanthanide ions: Synthesis, structural characterization, and photoluminescent behavior

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