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Title: Exploring the Promotion of Synthons of Choice: Halogen Bonding in Molecular Lanthanide Complexes Characterized via X-ray Diffraction, Luminescence Spectroscopy, and Magnetic Measurements

Abstract

Promotion of a synthon of choice for the non-covalent assembly of lanthanide tectons represents both a noteworthy challenge and opportunity within Ln(III) hybrid materials. We have developed a system wherein some control can be exercised over supramolecular assembly and, as part of continued efforts to improve this process we have generated a family of ten new lanthanide (Ln = Sm 3+-Lu 3+)-2,4,6-trichlorobenzoic acid-1,10- phenanthroline molecular complexes. Delineation of criteria for promoting assembly via halogen based interactions was introduced previously and is refined herein based on the characterization of complexes 1-10 via single crystal X-ray diffraction. Direct comparison of means of supramolecular assembly for 1-10 with isostructural Ln-pchlorobenzoic acid-1,10-phenathroline analogues verifies that increasing the number of halogens at the periphery of a tecton is one route that increases the frequency of halogen bonding interactions. Additionally, solid-state visible and near-IR photoluminescence and luminescent lifetime data were collected for complexes 1 (Sm 3+), 2 (Eu 3+), 4 (Tb 3+), 5 (Dy 3+), 6 (Ho 3+), 7 (Er 3+), and 9 (Yb 3+) and characteristic emission was observed for all complexes except 6. Further, direct current magnetic susceptibility measurements were carried out for complexes 5 (Dy 3+) and 7 (Er 3+), and two slowmore » magnetic relaxation processes were characterized using alternating current magnetic susceptibility measurements for 5.« less

Authors:
 [1];  [2];  [1];  [3];  [3];  [1]
  1. George Washington Univ., Washington, DC (United States). Dept. of Chemistry
  2. Cardiff Univ., Wales (United Kingdom). School of Chemistry
  3. Univ. of Ottawa, Ottawa, ON (Canada). Dept. of Chemistry and Biomolecular Sciences
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Materials Science of Actinides (MSA)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1470041
Alternate Identifier(s):
OSTI ID: 1399274
Grant/Contract Number:  
[SC0001089]
Resource Type:
Accepted Manuscript
Journal Name:
Zeitschrift fuer Anorganische und Allgemeine Chemie
Additional Journal Information:
[ Journal Volume: 643; Journal Issue: 23; Related Information: MSA partners with University of Notre Dame (lead); University of California, Davis; Florida State University; George Washington University; University of Michigan; University of Minnesota; Oak Ridge National Laboratory; Oregon state University; Rensselaer Polytechnic Institute; Savannah River National Laboratory]; Journal ID: ISSN 0044-2313
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE; nuclear (including radiation effects); materials and chemistry by design; synthesis (novel materials), synthesis (self-assembly)

Citation Formats

Carter, Korey P., Pope, Simon J. A., Kalaj, Mark, Holmberg, Rebecca J., Murugesu, Muralee, and Cahill, Christopher L. Exploring the Promotion of Synthons of Choice: Halogen Bonding in Molecular Lanthanide Complexes Characterized via X-ray Diffraction, Luminescence Spectroscopy, and Magnetic Measurements. United States: N. p., 2017. Web. doi:10.1002/zaac.201700341.
Carter, Korey P., Pope, Simon J. A., Kalaj, Mark, Holmberg, Rebecca J., Murugesu, Muralee, & Cahill, Christopher L. Exploring the Promotion of Synthons of Choice: Halogen Bonding in Molecular Lanthanide Complexes Characterized via X-ray Diffraction, Luminescence Spectroscopy, and Magnetic Measurements. United States. doi:10.1002/zaac.201700341.
Carter, Korey P., Pope, Simon J. A., Kalaj, Mark, Holmberg, Rebecca J., Murugesu, Muralee, and Cahill, Christopher L. Fri . "Exploring the Promotion of Synthons of Choice: Halogen Bonding in Molecular Lanthanide Complexes Characterized via X-ray Diffraction, Luminescence Spectroscopy, and Magnetic Measurements". United States. doi:10.1002/zaac.201700341. https://www.osti.gov/servlets/purl/1470041.
@article{osti_1470041,
title = {Exploring the Promotion of Synthons of Choice: Halogen Bonding in Molecular Lanthanide Complexes Characterized via X-ray Diffraction, Luminescence Spectroscopy, and Magnetic Measurements},
author = {Carter, Korey P. and Pope, Simon J. A. and Kalaj, Mark and Holmberg, Rebecca J. and Murugesu, Muralee and Cahill, Christopher L.},
abstractNote = {Promotion of a synthon of choice for the non-covalent assembly of lanthanide tectons represents both a noteworthy challenge and opportunity within Ln(III) hybrid materials. We have developed a system wherein some control can be exercised over supramolecular assembly and, as part of continued efforts to improve this process we have generated a family of ten new lanthanide (Ln = Sm3+-Lu3+)-2,4,6-trichlorobenzoic acid-1,10- phenanthroline molecular complexes. Delineation of criteria for promoting assembly via halogen based interactions was introduced previously and is refined herein based on the characterization of complexes 1-10 via single crystal X-ray diffraction. Direct comparison of means of supramolecular assembly for 1-10 with isostructural Ln-pchlorobenzoic acid-1,10-phenathroline analogues verifies that increasing the number of halogens at the periphery of a tecton is one route that increases the frequency of halogen bonding interactions. Additionally, solid-state visible and near-IR photoluminescence and luminescent lifetime data were collected for complexes 1 (Sm3+), 2 (Eu3+), 4 (Tb3+), 5 (Dy3+), 6 (Ho3+), 7 (Er3+), and 9 (Yb3+) and characteristic emission was observed for all complexes except 6. Further, direct current magnetic susceptibility measurements were carried out for complexes 5 (Dy3+) and 7 (Er3+), and two slow magnetic relaxation processes were characterized using alternating current magnetic susceptibility measurements for 5.},
doi = {10.1002/zaac.201700341},
journal = {Zeitschrift fuer Anorganische und Allgemeine Chemie},
number = [23],
volume = [643],
place = {United States},
year = {2017},
month = {9}
}

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Works referenced in this record:

RE-p-halobenzoic acid–terpyridine complexes, part III: structural and supramolecular trends in a series of p-iodobenzoic acid rare-earth hybrid materials
journal, January 2017

  • August Ridenour, J.; Carter, Korey P.; Cahill, Christopher L.
  • CrystEngComm, Vol. 19, Issue 8
  • DOI: 10.1039/C6CE02356H

Benzothiazole- and Benzoxazole-Substituted Pyridine-2-Carboxylates as Efficient Sensitizers of Europium Luminescence
journal, July 2009

  • Shavaleev, Nail M.; Scopelliti, Rosario; Gumy, Frédéric
  • Inorganic Chemistry, Vol. 48, Issue 13
  • DOI: 10.1021/ic9005136

The Halogen Bond
journal, January 2016


Nonlinear optical activity in dipolar organic–lanthanide complexes
journal, January 2010

  • Law, Ga-Lai; Wong, Ka-Leung; Lau, Kok-Kin
  • Journal of Materials Chemistry, Vol. 20, Issue 20
  • DOI: 10.1039/b926376d

OH–π and halogen–π interactions as driving forces in the crystal organisations of tri-bromo and tri-iodo trityl alcohols
journal, January 2008

  • Schollmeyer, Dieter; Shishkin, Oleg V.; Rühl, Thomas
  • CrystEngComm, Vol. 10, Issue 6
  • DOI: 10.1039/b716442d

Halogen Bonding in Supramolecular Chemistry
journal, July 2015

  • Gilday, Lydia C.; Robinson, Sean W.; Barendt, Timothy A.
  • Chemical Reviews, Vol. 115, Issue 15
  • DOI: 10.1021/cr500674c

Lanthanide-Containing Molecular and Supramolecular Polymetallic Functional Assemblies
journal, June 2002

  • Bünzli, Jean-Claude G.; Piguet, Claude
  • Chemical Reviews, Vol. 102, Issue 6
  • DOI: 10.1021/cr010299j

WinGX and ORTEP for Windows : an update
journal, July 2012


Comparison of silver and molybdenum microfocus X-ray sources for single-crystal structure determination
journal, January 2015

  • Krause, Lennard; Herbst-Irmer, Regine; Sheldrick, George M.
  • Journal of Applied Crystallography, Vol. 48, Issue 1
  • DOI: 10.1107/S1600576714022985

Lanthanide light for biology and medical diagnosis
journal, February 2016


Aromatic N-donor ligands as chelators and sensitizers of lanthanide ion emission
journal, August 2014

  • de Bettencourt-Dias, Ana; Barber, Patrick S.; Viswanathan, Subha
  • Coordination Chemistry Reviews, Vol. 273-274
  • DOI: 10.1016/j.ccr.2014.04.010

Surprisingly Bright Near-Infrared Luminescence and Short Radiative Lifetimes of Ytterbium in Hetero-Binuclear Yb−Na Chelates
journal, August 2009

  • Shavaleev, Nail M.; Scopelliti, Rosario; Gumy, Frédéric
  • Inorganic Chemistry, Vol. 48, Issue 16
  • DOI: 10.1021/ic900888m

NIR Lanthanide Luminescence by Energy Transfer from Appended Terpyridine–Boradiazaindacene Dyes
journal, June 2006

  • Ziessel, Raymond F.; Ulrich, Gilles; Charbonnière, Loïc
  • Chemistry - A European Journal, Vol. 12, Issue 19
  • DOI: 10.1002/chem.200600124

Halogen Bonds in Crystal Engineering: Like Hydrogen Bonds yet Different
journal, May 2014

  • Mukherjee, Arijit; Tothadi, Srinu; Desiraju, Gautam R.
  • Accounts of Chemical Research, Vol. 47, Issue 8
  • DOI: 10.1021/ar5001555

Lone pair–π interactions: a new supramolecular bond?
journal, January 2008

  • Mooibroek, Tiddo J.; Gamez, Patrick; Reedijk, Jan
  • CrystEngComm, Vol. 10, Issue 11
  • DOI: 10.1039/b812026a

Crystal structure refinement with SHELXL
journal, January 2015

  • Sheldrick, George M.
  • Acta Crystallographica Section C Structural Chemistry, Vol. 71, Issue 1, p. 3-8
  • DOI: 10.1107/S2053229614024218

The nature of halogen.cntdot..cntdot..cntdot.halogen interactions: are short halogen contacts due to specific attractive forces or due to close packing of nonspherical atoms?
journal, November 1989

  • Desiraju, Gautam R.; Parthasarathy, R.
  • Journal of the American Chemical Society, Vol. 111, Issue 23
  • DOI: 10.1021/ja00205a027

Structural Rearrangement Through Lanthanide Contraction in Dinuclear Complexes
journal, December 2013

  • Hutchings, Amy-Jayne; Habib, Fatemah; Holmberg, Rebecca J.
  • Inorganic Chemistry, Vol. 53, Issue 4
  • DOI: 10.1021/ic402682r

Eight rare earth metal organic frameworks and coordination polymers from 2-nitroterephthlate: syntheses, structures, solid-state luminescence and an unprecedented topology
journal, January 2016

  • Smith, Jermaine A.; Singh-Wilmot, Marvadeen A.; Carter, Korey P.
  • New Journal of Chemistry, Vol. 40, Issue 9
  • DOI: 10.1039/C6NJ00822D

Lanthanide luminescence efficiency in eight- and nine-coordinate complexes: Role of the radiative lifetime
journal, November 2010

  • Bünzli, Jean-Claude G.; Chauvin, Anne-Sophie; Kim, Hwan Kyu
  • Coordination Chemistry Reviews, Vol. 254, Issue 21-22
  • DOI: 10.1016/j.ccr.2010.04.002

Structural regularities and luminescence properties of dimeric europium and terbium carboxylates with 1,10-phenanthroline (C.N.=9)
journal, March 2010

  • Tsaryuk, Vera I.; Zhuravlev, Konstantin P.; Vologzhanina, Anna V.
  • Journal of Photochemistry and Photobiology A: Chemistry, Vol. 211, Issue 1
  • DOI: 10.1016/j.jphotochem.2010.01.012

Development of responsive visibly and NIR luminescent and supramolecular coordination self-assemblies using lanthanide ion directed synthesis
journal, August 2014

  • Bradberry, Samuel J.; Savyasachi, Aramballi Jayant; Martinez-Calvo, Miguel
  • Coordination Chemistry Reviews, Vol. 273-274
  • DOI: 10.1016/j.ccr.2014.03.023

Lanthanide Luminescent Bioprobes (LLBs)
journal, February 2009


Exploring supramolecular assembly and luminescent behavior in a series of RE-p-chlorobenzoic acid-1,10-phenanthroline complexes
journal, January 2014

  • Carter, Korey P.; Zulato, Cecília H. F.; Cahill, Christopher L.
  • CrystEngComm, Vol. 16, Issue 44
  • DOI: 10.1039/C4CE01806K

Chelating agents for radiolanthanides: Applications to imaging and therapy
journal, June 2017

  • Amoroso, Angelo J.; Fallis, Ian A.; Pope, Simon J. A.
  • Coordination Chemistry Reviews, Vol. 340
  • DOI: 10.1016/j.ccr.2017.01.010

Lanthanides in molecular magnetism: so fascinating, so challenging
journal, January 2012

  • Luzon, Javier; Sessoli, Roberta
  • Dalton Transactions, Vol. 41, Issue 44
  • DOI: 10.1039/c2dt31388j

Controlling dimensionality via a dual ligand strategy in Ln-thiophene-2,5-dicarboxylic acid-terpyridine coordination polymers
journal, January 2015

  • Carter, Korey P.; Zulato, Cecília H. F.; Rodrigues, Emille M.
  • Dalton Transactions, Vol. 44, Issue 36
  • DOI: 10.1039/C5DT02596F

Theoretical and Experimental Studies of the Photoluminescent Properties of the Coordination Polymer [Eu(DPA)(HDPA)(H 2 O) 2 ]·4H 2 O
journal, April 2008

  • Rodrigues, Marcelo O.; da Costa Júnior, Nivan B.; de Simone, Carlos A.
  • The Journal of Physical Chemistry B, Vol. 112, Issue 14
  • DOI: 10.1021/jp075047m

Lanthanide-directed synthesis of luminescent self-assembly supramolecular structures and mechanically bonded systems from acyclic coordinating organic ligands
journal, January 2016

  • Barry, Dawn E.; Caffrey, David F.; Gunnlaugsson, Thorfinnur
  • Chemical Society Reviews, Vol. 45, Issue 11
  • DOI: 10.1039/C6CS00116E

Lanthanide Single-Molecule Magnets
journal, March 2013

  • Woodruff, Daniel N.; Winpenny, Richard E. P.; Layfield, Richard A.
  • Chemical Reviews, Vol. 113, Issue 7
  • DOI: 10.1021/cr400018q

A series of Ln-p-chlorobenzoic acid–terpyridine complexes: lanthanide contraction effects, supramolecular interactions and luminescent behavior
journal, January 2014

  • Carter, Korey P.; Pope, Simon J. A.; Cahill, Christopher L.
  • CrystEngComm, Vol. 16, Issue 10
  • DOI: 10.1039/c3ce42267d

Functional luminescent lanthanide complexes: Modulation of visible luminescence from europium complexes
journal, August 2011


An Organolanthanide Building Block Approach to Single-Molecule Magnets
journal, May 2016


Nonlinear optical properties, upconversion and lasing in metal–organic frameworks
journal, January 2017

  • Medishetty, Raghavender; Zaręba, Jan K.; Mayer, David
  • Chemical Society Reviews, Vol. 46, Issue 16
  • DOI: 10.1039/C7CS00162B

    Works referencing / citing this record:

    NIR Lanthanide Luminescence by Energy Transfer from Appended Terpyridine–Boradiazaindacene Dyes
    journal, June 2006

    • Ziessel, Raymond F.; Ulrich, Gilles; Charbonnière, Loïc
    • Chemistry - A European Journal, Vol. 12, Issue 19
    • DOI: 10.1002/chem.200600124

    A Thorium Metal‐Organic Framework with Outstanding Thermal and Chemical Stability
    journal, April 2019

    • Carter, Korey P.; Ridenour, J. August; Kalaj, Mark
    • Chemistry – A European Journal, Vol. 25, Issue 29
    • DOI: 10.1002/chem.201901610

    Lanthanide luminescence efficiency in eight- and nine-coordinate complexes: Role of the radiative lifetime
    journal, November 2010

    • Bünzli, Jean-Claude G.; Chauvin, Anne-Sophie; Kim, Hwan Kyu
    • Coordination Chemistry Reviews, Vol. 254, Issue 21-22
    • DOI: 10.1016/j.ccr.2010.04.002

    Development of responsive visibly and NIR luminescent and supramolecular coordination self-assemblies using lanthanide ion directed synthesis
    journal, August 2014

    • Bradberry, Samuel J.; Savyasachi, Aramballi Jayant; Martinez-Calvo, Miguel
    • Coordination Chemistry Reviews, Vol. 273-274
    • DOI: 10.1016/j.ccr.2014.03.023

    Aromatic N-donor ligands as chelators and sensitizers of lanthanide ion emission
    journal, August 2014

    • de Bettencourt-Dias, Ana; Barber, Patrick S.; Viswanathan, Subha
    • Coordination Chemistry Reviews, Vol. 273-274
    • DOI: 10.1016/j.ccr.2014.04.010

    Chelating agents for radiolanthanides: Applications to imaging and therapy
    journal, June 2017

    • Amoroso, Angelo J.; Fallis, Ian A.; Pope, Simon J. A.
    • Coordination Chemistry Reviews, Vol. 340
    • DOI: 10.1016/j.ccr.2017.01.010

    Lanthanide light for biology and medical diagnosis
    journal, February 2016


    Structural regularities and luminescence properties of dimeric europium and terbium carboxylates with 1,10-phenanthroline (C.N.=9)
    journal, March 2010

    • Tsaryuk, Vera I.; Zhuravlev, Konstantin P.; Vologzhanina, Anna V.
    • Journal of Photochemistry and Photobiology A: Chemistry, Vol. 211, Issue 1
    • DOI: 10.1016/j.jphotochem.2010.01.012

    Functional luminescent lanthanide complexes: Modulation of visible luminescence from europium complexes
    journal, August 2011


    An Organolanthanide Building Block Approach to Single-Molecule Magnets
    journal, May 2016


    The Halogen Bond
    journal, January 2016


    Halogen Bonds in Crystal Engineering: Like Hydrogen Bonds yet Different
    journal, May 2014

    • Mukherjee, Arijit; Tothadi, Srinu; Desiraju, Gautam R.
    • Accounts of Chemical Research, Vol. 47, Issue 8
    • DOI: 10.1021/ar5001555

    Lanthanide-Containing Molecular and Supramolecular Polymetallic Functional Assemblies
    journal, June 2002

    • Bünzli, Jean-Claude G.; Piguet, Claude
    • Chemical Reviews, Vol. 102, Issue 6
    • DOI: 10.1021/cr010299j

    Lanthanide Single-Molecule Magnets
    journal, March 2013

    • Woodruff, Daniel N.; Winpenny, Richard E. P.; Layfield, Richard A.
    • Chemical Reviews, Vol. 113, Issue 7
    • DOI: 10.1021/cr400018q

    Halogen Bonding in Supramolecular Chemistry
    journal, July 2015

    • Gilday, Lydia C.; Robinson, Sean W.; Barendt, Timothy A.
    • Chemical Reviews, Vol. 115, Issue 15
    • DOI: 10.1021/cr500674c

    Structural Rearrangement Through Lanthanide Contraction in Dinuclear Complexes
    journal, December 2013

    • Hutchings, Amy-Jayne; Habib, Fatemah; Holmberg, Rebecca J.
    • Inorganic Chemistry, Vol. 53, Issue 4
    • DOI: 10.1021/ic402682r

    Benzothiazole- and Benzoxazole-Substituted Pyridine-2-Carboxylates as Efficient Sensitizers of Europium Luminescence
    journal, July 2009

    • Shavaleev, Nail M.; Scopelliti, Rosario; Gumy, Frédéric
    • Inorganic Chemistry, Vol. 48, Issue 13
    • DOI: 10.1021/ic9005136

    Surprisingly Bright Near-Infrared Luminescence and Short Radiative Lifetimes of Ytterbium in Hetero-Binuclear Yb−Na Chelates
    journal, August 2009

    • Shavaleev, Nail M.; Scopelliti, Rosario; Gumy, Frédéric
    • Inorganic Chemistry, Vol. 48, Issue 16
    • DOI: 10.1021/ic900888m

    The nature of halogen.cntdot..cntdot..cntdot.halogen interactions: are short halogen contacts due to specific attractive forces or due to close packing of nonspherical atoms?
    journal, November 1989

    • Desiraju, Gautam R.; Parthasarathy, R.
    • Journal of the American Chemical Society, Vol. 111, Issue 23
    • DOI: 10.1021/ja00205a027

    Theoretical and Experimental Studies of the Photoluminescent Properties of the Coordination Polymer [Eu(DPA)(HDPA)(H 2 O) 2 ]·4H 2 O
    journal, April 2008

    • Rodrigues, Marcelo O.; da Costa Júnior, Nivan B.; de Simone, Carlos A.
    • The Journal of Physical Chemistry B, Vol. 112, Issue 14
    • DOI: 10.1021/jp075047m

    OH–π and halogen–π interactions as driving forces in the crystal organisations of tri-bromo and tri-iodo trityl alcohols
    journal, January 2008

    • Schollmeyer, Dieter; Shishkin, Oleg V.; Rühl, Thomas
    • CrystEngComm, Vol. 10, Issue 6
    • DOI: 10.1039/b716442d

    Lone pair–π interactions: a new supramolecular bond?
    journal, January 2008

    • Mooibroek, Tiddo J.; Gamez, Patrick; Reedijk, Jan
    • CrystEngComm, Vol. 10, Issue 11
    • DOI: 10.1039/b812026a

    Nonlinear optical activity in dipolar organic–lanthanide complexes
    journal, January 2010

    • Law, Ga-Lai; Wong, Ka-Leung; Lau, Kok-Kin
    • Journal of Materials Chemistry, Vol. 20, Issue 20
    • DOI: 10.1039/b926376d

    Lanthanides in molecular magnetism: so fascinating, so challenging
    journal, January 2012

    • Luzon, Javier; Sessoli, Roberta
    • Dalton Transactions, Vol. 41, Issue 44
    • DOI: 10.1039/c2dt31388j

    A series of Ln-p-chlorobenzoic acid–terpyridine complexes: lanthanide contraction effects, supramolecular interactions and luminescent behavior
    journal, January 2014

    • Carter, Korey P.; Pope, Simon J. A.; Cahill, Christopher L.
    • CrystEngComm, Vol. 16, Issue 10
    • DOI: 10.1039/c3ce42267d

    Lanthanide Luminescent Bioprobes (LLBs)
    journal, February 2009