An unprecedented two-dimensional polymeric [Zn(OOC-C6H4-COO)2]n 2-[+H3N-(CH2)3-NH3 +]n system bearing one-dimensional chain of zinc(II) bis(phthalate) dianions held by propane-1,3-diammonium cations: Crystal structure, thermal and fluorescent properties

M. Padmanabhan, K. C. Joseph, Vedavati G. Puranik, Xiaoying Huang, Jing Li

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Abstract

A novel zinc(II) phthalate compound, [Zn{C6H4(COO)2}2]n 2-[NH3-(CH2)3-NH3]n 2+, 1 which contains four different phthalate moieties coordinated to the Zn(II) ion through one each of their carboxylate moieties in a η1-form and each phthalate moiety acting as a bridging unit with an overall tetrahedral geometry around the metal ion has been prepared and structurally characterized. The structure is unique in the sense that the dianionic moieties [Zn{C6H4(COO)2}2]2- form an infinite one-dimensional network composed of 14-membered cyclic units interconnected in a way that they are disposed alternatively in almost perpendicular planes. The dicationic [NH3-(CH2)3-NH3]2+ units are seen to hold these one-dimensional chains by strong coulombic and hydrogen bond interaction, resulting in an infinite two-dimensional layered structure of 1. The compound is thermally stable up to 250 °C. Above this temperature it loses one equivalent of phthalate moiety along with the diammonium unit to yield Zn(II) phthalate. The thermodynamic and kinetic parameters associated with this process could be evaluated using Coats-Redfern equation which shows the activation energy Ea for the process as 305.0 kJ mol-1, the frequency factor A as 1.49 × 1011 s-1 and the entropy change ΔS as -35.90 JK-1 mol-1. Fluorescent emission properties of 1 was studied by exciting the compound at 380 nm and also at 322 nm which were found to be the two λmax corresponding to absorptions of the molecule. Interestingly, the compound gave same type of emission spectra showing a maximum around 444 nm on exciting at these two different wavelengths, indicating that the molecule comes to the first excited state from the higher excited state by a fast non-radiative process before it exhibits singlet emission to come to the ground state.

Original languageEnglish
Pages (from-to)491-495
Number of pages5
JournalSolid State Sciences
Volume9
Issue number6
DOIs
Publication statusPublished - Jun 2007

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Bearings (structural)
Propane
phthalates
Excited states
propane
Cations
Zinc
thermodynamic properties
zinc
Crystal structure
Positive ions
cations
crystal structure
Molecules
Kinetic parameters
Ground state
Metal ions
Hydrogen bonds
Entropy
Activation energy

Keywords

  • Cyclic chain
  • Fluorescent emission
  • Layered structure
  • Propane-1,3-diammonium
  • Zinc(II) bis(phthalate) dianion
  • Zinc-phthalate

ASJC Scopus subject areas

  • Ceramics and Composites
  • Materials Chemistry

Cite this

@article{c322755b0f86480d9082618516ae9f3a,
title = "An unprecedented two-dimensional polymeric [Zn(OOC-C6H4-COO)2]n 2-[+H3N-(CH2)3-NH3 +]n system bearing one-dimensional chain of zinc(II) bis(phthalate) dianions held by propane-1,3-diammonium cations: Crystal structure, thermal and fluorescent properties",
abstract = "A novel zinc(II) phthalate compound, [Zn{C6H4(COO)2}2]n 2-[NH3-(CH2)3-NH3]n 2+, 1 which contains four different phthalate moieties coordinated to the Zn(II) ion through one each of their carboxylate moieties in a η1-form and each phthalate moiety acting as a bridging unit with an overall tetrahedral geometry around the metal ion has been prepared and structurally characterized. The structure is unique in the sense that the dianionic moieties [Zn{C6H4(COO)2}2]2- form an infinite one-dimensional network composed of 14-membered cyclic units interconnected in a way that they are disposed alternatively in almost perpendicular planes. The dicationic [NH3-(CH2)3-NH3]2+ units are seen to hold these one-dimensional chains by strong coulombic and hydrogen bond interaction, resulting in an infinite two-dimensional layered structure of 1. The compound is thermally stable up to 250 °C. Above this temperature it loses one equivalent of phthalate moiety along with the diammonium unit to yield Zn(II) phthalate. The thermodynamic and kinetic parameters associated with this process could be evaluated using Coats-Redfern equation which shows the activation energy Ea for the process as 305.0 kJ mol-1, the frequency factor A as 1.49 × 1011 s-1 and the entropy change ΔS as -35.90 JK-1 mol-1. Fluorescent emission properties of 1 was studied by exciting the compound at 380 nm and also at 322 nm which were found to be the two λmax corresponding to absorptions of the molecule. Interestingly, the compound gave same type of emission spectra showing a maximum around 444 nm on exciting at these two different wavelengths, indicating that the molecule comes to the first excited state from the higher excited state by a fast non-radiative process before it exhibits singlet emission to come to the ground state.",
keywords = "Cyclic chain, Fluorescent emission, Layered structure, Propane-1,3-diammonium, Zinc(II) bis(phthalate) dianion, Zinc-phthalate",
author = "M. Padmanabhan and Joseph, {K. C.} and Puranik, {Vedavati G.} and Xiaoying Huang and Jing Li",
year = "2007",
month = "6",
doi = "10.1016/j.solidstatesciences.2007.04.009",
language = "English",
volume = "9",
pages = "491--495",
journal = "Solid State Sciences",
issn = "1293-2558",
publisher = "Elsevier Masson SAS",
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TY - JOUR

T1 - An unprecedented two-dimensional polymeric [Zn(OOC-C6H4-COO)2]n 2-[+H3N-(CH2)3-NH3 +]n system bearing one-dimensional chain of zinc(II) bis(phthalate) dianions held by propane-1,3-diammonium cations

T2 - Crystal structure, thermal and fluorescent properties

AU - Padmanabhan, M.

AU - Joseph, K. C.

AU - Puranik, Vedavati G.

AU - Huang, Xiaoying

AU - Li, Jing

PY - 2007/6

Y1 - 2007/6

N2 - A novel zinc(II) phthalate compound, [Zn{C6H4(COO)2}2]n 2-[NH3-(CH2)3-NH3]n 2+, 1 which contains four different phthalate moieties coordinated to the Zn(II) ion through one each of their carboxylate moieties in a η1-form and each phthalate moiety acting as a bridging unit with an overall tetrahedral geometry around the metal ion has been prepared and structurally characterized. The structure is unique in the sense that the dianionic moieties [Zn{C6H4(COO)2}2]2- form an infinite one-dimensional network composed of 14-membered cyclic units interconnected in a way that they are disposed alternatively in almost perpendicular planes. The dicationic [NH3-(CH2)3-NH3]2+ units are seen to hold these one-dimensional chains by strong coulombic and hydrogen bond interaction, resulting in an infinite two-dimensional layered structure of 1. The compound is thermally stable up to 250 °C. Above this temperature it loses one equivalent of phthalate moiety along with the diammonium unit to yield Zn(II) phthalate. The thermodynamic and kinetic parameters associated with this process could be evaluated using Coats-Redfern equation which shows the activation energy Ea for the process as 305.0 kJ mol-1, the frequency factor A as 1.49 × 1011 s-1 and the entropy change ΔS as -35.90 JK-1 mol-1. Fluorescent emission properties of 1 was studied by exciting the compound at 380 nm and also at 322 nm which were found to be the two λmax corresponding to absorptions of the molecule. Interestingly, the compound gave same type of emission spectra showing a maximum around 444 nm on exciting at these two different wavelengths, indicating that the molecule comes to the first excited state from the higher excited state by a fast non-radiative process before it exhibits singlet emission to come to the ground state.

AB - A novel zinc(II) phthalate compound, [Zn{C6H4(COO)2}2]n 2-[NH3-(CH2)3-NH3]n 2+, 1 which contains four different phthalate moieties coordinated to the Zn(II) ion through one each of their carboxylate moieties in a η1-form and each phthalate moiety acting as a bridging unit with an overall tetrahedral geometry around the metal ion has been prepared and structurally characterized. The structure is unique in the sense that the dianionic moieties [Zn{C6H4(COO)2}2]2- form an infinite one-dimensional network composed of 14-membered cyclic units interconnected in a way that they are disposed alternatively in almost perpendicular planes. The dicationic [NH3-(CH2)3-NH3]2+ units are seen to hold these one-dimensional chains by strong coulombic and hydrogen bond interaction, resulting in an infinite two-dimensional layered structure of 1. The compound is thermally stable up to 250 °C. Above this temperature it loses one equivalent of phthalate moiety along with the diammonium unit to yield Zn(II) phthalate. The thermodynamic and kinetic parameters associated with this process could be evaluated using Coats-Redfern equation which shows the activation energy Ea for the process as 305.0 kJ mol-1, the frequency factor A as 1.49 × 1011 s-1 and the entropy change ΔS as -35.90 JK-1 mol-1. Fluorescent emission properties of 1 was studied by exciting the compound at 380 nm and also at 322 nm which were found to be the two λmax corresponding to absorptions of the molecule. Interestingly, the compound gave same type of emission spectra showing a maximum around 444 nm on exciting at these two different wavelengths, indicating that the molecule comes to the first excited state from the higher excited state by a fast non-radiative process before it exhibits singlet emission to come to the ground state.

KW - Cyclic chain

KW - Fluorescent emission

KW - Layered structure

KW - Propane-1,3-diammonium

KW - Zinc(II) bis(phthalate) dianion

KW - Zinc-phthalate

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U2 - 10.1016/j.solidstatesciences.2007.04.009

DO - 10.1016/j.solidstatesciences.2007.04.009

M3 - Article

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EP - 495

JO - Solid State Sciences

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