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Title: Concentration Dependent Dimensionality of Resonance Energy Transfer in a Postsynthetically Doped Morphologically Homologous Analogue of UiO-67 MOF with a Ruthenium(II) Polypyridyl Complex

Abstract

In this study, a method is described here by which to dope ruthenium(II) bis(2,2'-bipyridine) (2,2'-bipyridyl-5,5'-dicarboxylic acid), RuDCBPY, into a UiO-67 metal–organic framework (MOF) derivative in which 2,2'-bipyridyl-5,5'-dicarboxylic acid, UiO-67-DCBPY, is used in place of 4,4'-biphenyldicarboxylic acid. Emission lifetime measurements of the RuDCBPY triplet metal-to-ligand charge transfer, 3MLCT, excited state as a function of RuDCBPY doping concentration in UiO-67-DCBPY are discussed in light of previous results for RuDCBPY-UiO-67 doped powders in which quenching of the 3MLCT was said to be due to dipole–dipole homogeneous resonance energy transfer, RET. The bulk distribution of RuDCBPY centers within MOF crystallites are also estimated with the use of confocal fluorescence microscopy. In the present case, it is assumed that the rate of RET between RuDCBPY centers has an r–6 separation distance dependence characteristic of Förster RET. The results suggest (1) the dimensionality in which RET occurs is dependent on the RuDCBPY concentration ranging from one-dimensional at very low concentrations up to three-dimensional at high concentration, (2) the occupancy of RuDCBPY within UiO-67-DCBPY is not uniform throughout the crystallites such that RuDCBPY densely populates the outer layers of the MOF at low concentrations, and (3) the average separation distance between RuDCBPY centers is ~21 Å.

Authors:
 [1];  [1];  [1]
  1. Department of Chemistry, Virginia Polytechnic Institute and State University, Blacksburg, Virginia 24061, United States
Publication Date:
Research Org.:
Virginia Polytechnic Inst. and State Univ. (Virginia Tech), Blacksburg, VA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1185241
Alternate Identifier(s):
OSTI ID: 1454259
Grant/Contract Number:  
SN20074; SC0012446
Resource Type:
Published Article
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Name: Journal of the American Chemical Society Journal Volume: 137 Journal Issue: 25; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Maza, William A., Padilla, Roberto, and Morris, Amanda J. Concentration Dependent Dimensionality of Resonance Energy Transfer in a Postsynthetically Doped Morphologically Homologous Analogue of UiO-67 MOF with a Ruthenium(II) Polypyridyl Complex. United States: N. p., 2015. Web. doi:10.1021/jacs.5b03071.
Maza, William A., Padilla, Roberto, & Morris, Amanda J. Concentration Dependent Dimensionality of Resonance Energy Transfer in a Postsynthetically Doped Morphologically Homologous Analogue of UiO-67 MOF with a Ruthenium(II) Polypyridyl Complex. United States. doi:10.1021/jacs.5b03071.
Maza, William A., Padilla, Roberto, and Morris, Amanda J. Thu . "Concentration Dependent Dimensionality of Resonance Energy Transfer in a Postsynthetically Doped Morphologically Homologous Analogue of UiO-67 MOF with a Ruthenium(II) Polypyridyl Complex". United States. doi:10.1021/jacs.5b03071.
@article{osti_1185241,
title = {Concentration Dependent Dimensionality of Resonance Energy Transfer in a Postsynthetically Doped Morphologically Homologous Analogue of UiO-67 MOF with a Ruthenium(II) Polypyridyl Complex},
author = {Maza, William A. and Padilla, Roberto and Morris, Amanda J.},
abstractNote = {In this study, a method is described here by which to dope ruthenium(II) bis(2,2'-bipyridine) (2,2'-bipyridyl-5,5'-dicarboxylic acid), RuDCBPY, into a UiO-67 metal–organic framework (MOF) derivative in which 2,2'-bipyridyl-5,5'-dicarboxylic acid, UiO-67-DCBPY, is used in place of 4,4'-biphenyldicarboxylic acid. Emission lifetime measurements of the RuDCBPY triplet metal-to-ligand charge transfer, 3MLCT, excited state as a function of RuDCBPY doping concentration in UiO-67-DCBPY are discussed in light of previous results for RuDCBPY-UiO-67 doped powders in which quenching of the 3MLCT was said to be due to dipole–dipole homogeneous resonance energy transfer, RET. The bulk distribution of RuDCBPY centers within MOF crystallites are also estimated with the use of confocal fluorescence microscopy. In the present case, it is assumed that the rate of RET between RuDCBPY centers has an r–6 separation distance dependence characteristic of Förster RET. The results suggest (1) the dimensionality in which RET occurs is dependent on the RuDCBPY concentration ranging from one-dimensional at very low concentrations up to three-dimensional at high concentration, (2) the occupancy of RuDCBPY within UiO-67-DCBPY is not uniform throughout the crystallites such that RuDCBPY densely populates the outer layers of the MOF at low concentrations, and (3) the average separation distance between RuDCBPY centers is ~21 Å.},
doi = {10.1021/jacs.5b03071},
journal = {Journal of the American Chemical Society},
number = 25,
volume = 137,
place = {United States},
year = {2015},
month = {6}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
DOI: 10.1021/jacs.5b03071

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Works referencing / citing this record:

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  • Wang, Lei; Xie, Zhigang; Dang, Song
  • Chemistry - A European Journal, Vol. 23, Issue 12
  • DOI: 10.1002/chem.201604869

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  • Maza, W. A.; Haring, A. J.; Ahrenholtz, S. R.
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journal, January 2018

  • Cui, Yuanjing; Zhang, Jun; He, Huajun
  • Chemical Society Reviews, Vol. 47, Issue 15
  • DOI: 10.1039/c7cs00879a

A luminescent [Pd 4 Ru 8 ] 24+ supramolecular cage
journal, January 2018

  • Rota Martir, Diego; Cordes, David B.; Slawin, Alexandra M. Z.
  • Chemical Communications, Vol. 54, Issue 47
  • DOI: 10.1039/c8cc02104j

Post-synthetic exchange (PSE) of UiO-67 frameworks with Ru/Rh half-sandwich units for visible-light-driven H 2 evolution and CO 2 reduction
journal, January 2018

  • Liao, Wei-Ming; Zhang, Jian-Hua; Wang, Zheng
  • Journal of Materials Chemistry A, Vol. 6, Issue 24
  • DOI: 10.1039/c8ta02962h

Construction of metal–organic frameworks from 3-(6-oxo-6,9-dihydro-1H-purin-1-yl)propionate
journal, July 2017