1-D helical chain, 2-D layered network and 3-D porous lanthanide-organic frameworks based on multiple coordination sites of benzimidazole-5,6- dicarboxylic acid: Synthesis, crystal structure, photoluminescence and thermal stability

Ping Wang, Rui Qing Fan, Yu Lin Yang, Xin Rong Liu, Peng Xiao, Xin Yu Li, Wuliji Hasi, Wen Wu Cao

Research output: Contribution to journalArticle

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Abstract

One-dimensional to three-dimensional lanthanide coordination polymers 1-8 based on benzimidazole-5,6-dicarboxylic acid (H3BIDC) have been synthesized under hydrothermal conditions at different pH values, generally formulated as {[Pr(HBIDC)(ox)0.5(H2O)]·H 2O}n (1), [Yb(HBIDC)(ox)0.5(H 2O)2]n (2), and [Ln(HBIDC)(ox) 0.5(H2O)3]n [Ln = Ho (3), and Tb (4)] and {[Ln(H2BIDC)(HBIDC)(H2O)3] ·3H2O}n [Ln = Tb (5), Sm (6), Dy (7), and Gd (8), H2ox = oxalic acid]. All coordination polymers have been characterized by elemental analysis, infrared spectra and single-crystal X-ray diffraction. The structural diversity, luminescence and thermal properties of all coordination polymers have been investigated. Coordination polymers 1-8 exhibit four different structural types: topological analysis has given the 3-D pcu network, with the point symbol of {412·63} in coordination polymer 1. Coordination polymer 2 exhibits a 4-connected 4 4 topology, and coordination polymers 3-4 appear as 2-D (6,3)-connected hcb network topology. The 1-D helical infinite chain of coordination polymers 5-8 around the crystallographic 21 axis spread along the b axis direction, with different 1-D helical infinite chains forming 3-D supramolecular framework via hydrogen bonds and π-π stacking interactions. The coordination polymers 4 and 5 could be triggered to have intense characteristic lanthanide-centered green luminescence under UV excitation in the solid state at room and liquid nitrogen temperature, or dispersed in CH2Cl2 at 77 K. In coordination polymers 4 and 5, the oxalic acid introduced into coordination polymer 4 as a second ligand further sensitized the trivalent terbium ion, and resulted in longer fluorescence lifetimes of coordination polymer 4 (1058.58 μs at 298 K, 679.42 μs at 77 K in the solid-state, 867.82 μs in CH2Cl2 at 77 K) than coordination polymer 5 (595.06 μs at 298 K, 583.19 μs at 77 K in the solid-state, 584.38 μs in CH2Cl2 at 77 K). In coordination polymers 6 and 7, we not only measured emission spectra in the visible region, but also detected the infrequent NIR emission spectra in the near infrared region of samarium and dysprosium ions. The singlet excited state (30 303 cm-1) and the lowest triplet state energy level (24 390 cm-1) of H3BIDC ligand were calculated based on the UV-vis absorbance edges of ligand and the phosphorescence spectrum of Gd(iii) coordination polymer (8) at 77 K, showing that the effective extent of energy transfer from H3BIDC ligand to lanthanide ions follows the sequence of Tb3+, Dy3+ > Sm3+. Finally, thermal behaviors of all coordination polymers were studied by thermogravimetric analysis, which exhibited high thermal stability.

Original languageEnglish (US)
Pages (from-to)4489-4506
Number of pages18
JournalCrystEngComm
Volume15
Issue number22
DOIs
StatePublished - Jun 14 2013

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Lanthanoid Series Elements
Dicarboxylic Acids
dicarboxylic acids
Rare earth elements
coordination polymers
Photoluminescence
Polymers
Thermodynamic stability
thermal stability
Crystal structure
photoluminescence
crystal structure
Acids
synthesis
Ligands
Oxalic Acid
ligands
oxalic acid
Oxalic acid
benzimidazole

All Science Journal Classification (ASJC) codes

  • Chemistry(all)
  • Materials Science(all)
  • Condensed Matter Physics

Cite this

@article{27e5bdeb959742a2a57772ca387ef0f0,
title = "1-D helical chain, 2-D layered network and 3-D porous lanthanide-organic frameworks based on multiple coordination sites of benzimidazole-5,6- dicarboxylic acid: Synthesis, crystal structure, photoluminescence and thermal stability",
abstract = "One-dimensional to three-dimensional lanthanide coordination polymers 1-8 based on benzimidazole-5,6-dicarboxylic acid (H3BIDC) have been synthesized under hydrothermal conditions at different pH values, generally formulated as {[Pr(HBIDC)(ox)0.5(H2O)]·H 2O}n (1), [Yb(HBIDC)(ox)0.5(H 2O)2]n (2), and [Ln(HBIDC)(ox) 0.5(H2O)3]n [Ln = Ho (3), and Tb (4)] and {[Ln(H2BIDC)(HBIDC)(H2O)3] ·3H2O}n [Ln = Tb (5), Sm (6), Dy (7), and Gd (8), H2ox = oxalic acid]. All coordination polymers have been characterized by elemental analysis, infrared spectra and single-crystal X-ray diffraction. The structural diversity, luminescence and thermal properties of all coordination polymers have been investigated. Coordination polymers 1-8 exhibit four different structural types: topological analysis has given the 3-D pcu network, with the point symbol of {412·63} in coordination polymer 1. Coordination polymer 2 exhibits a 4-connected 4 4 topology, and coordination polymers 3-4 appear as 2-D (6,3)-connected hcb network topology. The 1-D helical infinite chain of coordination polymers 5-8 around the crystallographic 21 axis spread along the b axis direction, with different 1-D helical infinite chains forming 3-D supramolecular framework via hydrogen bonds and π-π stacking interactions. The coordination polymers 4 and 5 could be triggered to have intense characteristic lanthanide-centered green luminescence under UV excitation in the solid state at room and liquid nitrogen temperature, or dispersed in CH2Cl2 at 77 K. In coordination polymers 4 and 5, the oxalic acid introduced into coordination polymer 4 as a second ligand further sensitized the trivalent terbium ion, and resulted in longer fluorescence lifetimes of coordination polymer 4 (1058.58 μs at 298 K, 679.42 μs at 77 K in the solid-state, 867.82 μs in CH2Cl2 at 77 K) than coordination polymer 5 (595.06 μs at 298 K, 583.19 μs at 77 K in the solid-state, 584.38 μs in CH2Cl2 at 77 K). In coordination polymers 6 and 7, we not only measured emission spectra in the visible region, but also detected the infrequent NIR emission spectra in the near infrared region of samarium and dysprosium ions. The singlet excited state (30 303 cm-1) and the lowest triplet state energy level (24 390 cm-1) of H3BIDC ligand were calculated based on the UV-vis absorbance edges of ligand and the phosphorescence spectrum of Gd(iii) coordination polymer (8) at 77 K, showing that the effective extent of energy transfer from H3BIDC ligand to lanthanide ions follows the sequence of Tb3+, Dy3+ > Sm3+. Finally, thermal behaviors of all coordination polymers were studied by thermogravimetric analysis, which exhibited high thermal stability.",
author = "Ping Wang and Fan, {Rui Qing} and Yang, {Yu Lin} and Liu, {Xin Rong} and Peng Xiao and Li, {Xin Yu} and Wuliji Hasi and Cao, {Wen Wu}",
year = "2013",
month = "6",
day = "14",
doi = "10.1039/c3ce40184g",
language = "English (US)",
volume = "15",
pages = "4489--4506",
journal = "CrystEngComm",
issn = "1466-8033",
publisher = "Royal Society of Chemistry",
number = "22",

}

1-D helical chain, 2-D layered network and 3-D porous lanthanide-organic frameworks based on multiple coordination sites of benzimidazole-5,6- dicarboxylic acid : Synthesis, crystal structure, photoluminescence and thermal stability. / Wang, Ping; Fan, Rui Qing; Yang, Yu Lin; Liu, Xin Rong; Xiao, Peng; Li, Xin Yu; Hasi, Wuliji; Cao, Wen Wu.

In: CrystEngComm, Vol. 15, No. 22, 14.06.2013, p. 4489-4506.

Research output: Contribution to journalArticle

TY - JOUR

T1 - 1-D helical chain, 2-D layered network and 3-D porous lanthanide-organic frameworks based on multiple coordination sites of benzimidazole-5,6- dicarboxylic acid

T2 - Synthesis, crystal structure, photoluminescence and thermal stability

AU - Wang, Ping

AU - Fan, Rui Qing

AU - Yang, Yu Lin

AU - Liu, Xin Rong

AU - Xiao, Peng

AU - Li, Xin Yu

AU - Hasi, Wuliji

AU - Cao, Wen Wu

PY - 2013/6/14

Y1 - 2013/6/14

N2 - One-dimensional to three-dimensional lanthanide coordination polymers 1-8 based on benzimidazole-5,6-dicarboxylic acid (H3BIDC) have been synthesized under hydrothermal conditions at different pH values, generally formulated as {[Pr(HBIDC)(ox)0.5(H2O)]·H 2O}n (1), [Yb(HBIDC)(ox)0.5(H 2O)2]n (2), and [Ln(HBIDC)(ox) 0.5(H2O)3]n [Ln = Ho (3), and Tb (4)] and {[Ln(H2BIDC)(HBIDC)(H2O)3] ·3H2O}n [Ln = Tb (5), Sm (6), Dy (7), and Gd (8), H2ox = oxalic acid]. All coordination polymers have been characterized by elemental analysis, infrared spectra and single-crystal X-ray diffraction. The structural diversity, luminescence and thermal properties of all coordination polymers have been investigated. Coordination polymers 1-8 exhibit four different structural types: topological analysis has given the 3-D pcu network, with the point symbol of {412·63} in coordination polymer 1. Coordination polymer 2 exhibits a 4-connected 4 4 topology, and coordination polymers 3-4 appear as 2-D (6,3)-connected hcb network topology. The 1-D helical infinite chain of coordination polymers 5-8 around the crystallographic 21 axis spread along the b axis direction, with different 1-D helical infinite chains forming 3-D supramolecular framework via hydrogen bonds and π-π stacking interactions. The coordination polymers 4 and 5 could be triggered to have intense characteristic lanthanide-centered green luminescence under UV excitation in the solid state at room and liquid nitrogen temperature, or dispersed in CH2Cl2 at 77 K. In coordination polymers 4 and 5, the oxalic acid introduced into coordination polymer 4 as a second ligand further sensitized the trivalent terbium ion, and resulted in longer fluorescence lifetimes of coordination polymer 4 (1058.58 μs at 298 K, 679.42 μs at 77 K in the solid-state, 867.82 μs in CH2Cl2 at 77 K) than coordination polymer 5 (595.06 μs at 298 K, 583.19 μs at 77 K in the solid-state, 584.38 μs in CH2Cl2 at 77 K). In coordination polymers 6 and 7, we not only measured emission spectra in the visible region, but also detected the infrequent NIR emission spectra in the near infrared region of samarium and dysprosium ions. The singlet excited state (30 303 cm-1) and the lowest triplet state energy level (24 390 cm-1) of H3BIDC ligand were calculated based on the UV-vis absorbance edges of ligand and the phosphorescence spectrum of Gd(iii) coordination polymer (8) at 77 K, showing that the effective extent of energy transfer from H3BIDC ligand to lanthanide ions follows the sequence of Tb3+, Dy3+ > Sm3+. Finally, thermal behaviors of all coordination polymers were studied by thermogravimetric analysis, which exhibited high thermal stability.

AB - One-dimensional to three-dimensional lanthanide coordination polymers 1-8 based on benzimidazole-5,6-dicarboxylic acid (H3BIDC) have been synthesized under hydrothermal conditions at different pH values, generally formulated as {[Pr(HBIDC)(ox)0.5(H2O)]·H 2O}n (1), [Yb(HBIDC)(ox)0.5(H 2O)2]n (2), and [Ln(HBIDC)(ox) 0.5(H2O)3]n [Ln = Ho (3), and Tb (4)] and {[Ln(H2BIDC)(HBIDC)(H2O)3] ·3H2O}n [Ln = Tb (5), Sm (6), Dy (7), and Gd (8), H2ox = oxalic acid]. All coordination polymers have been characterized by elemental analysis, infrared spectra and single-crystal X-ray diffraction. The structural diversity, luminescence and thermal properties of all coordination polymers have been investigated. Coordination polymers 1-8 exhibit four different structural types: topological analysis has given the 3-D pcu network, with the point symbol of {412·63} in coordination polymer 1. Coordination polymer 2 exhibits a 4-connected 4 4 topology, and coordination polymers 3-4 appear as 2-D (6,3)-connected hcb network topology. The 1-D helical infinite chain of coordination polymers 5-8 around the crystallographic 21 axis spread along the b axis direction, with different 1-D helical infinite chains forming 3-D supramolecular framework via hydrogen bonds and π-π stacking interactions. The coordination polymers 4 and 5 could be triggered to have intense characteristic lanthanide-centered green luminescence under UV excitation in the solid state at room and liquid nitrogen temperature, or dispersed in CH2Cl2 at 77 K. In coordination polymers 4 and 5, the oxalic acid introduced into coordination polymer 4 as a second ligand further sensitized the trivalent terbium ion, and resulted in longer fluorescence lifetimes of coordination polymer 4 (1058.58 μs at 298 K, 679.42 μs at 77 K in the solid-state, 867.82 μs in CH2Cl2 at 77 K) than coordination polymer 5 (595.06 μs at 298 K, 583.19 μs at 77 K in the solid-state, 584.38 μs in CH2Cl2 at 77 K). In coordination polymers 6 and 7, we not only measured emission spectra in the visible region, but also detected the infrequent NIR emission spectra in the near infrared region of samarium and dysprosium ions. The singlet excited state (30 303 cm-1) and the lowest triplet state energy level (24 390 cm-1) of H3BIDC ligand were calculated based on the UV-vis absorbance edges of ligand and the phosphorescence spectrum of Gd(iii) coordination polymer (8) at 77 K, showing that the effective extent of energy transfer from H3BIDC ligand to lanthanide ions follows the sequence of Tb3+, Dy3+ > Sm3+. Finally, thermal behaviors of all coordination polymers were studied by thermogravimetric analysis, which exhibited high thermal stability.

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