Luminescent Properties of DOBDC Containing MOFs: The Role of Free Hydroxyls

Henkelis, Susan E.; Rademacher, David; Vogel, Dayton J.; Valdez, Nichole R.; Rodriguez, Mark A.; Rohwer, Lauren E.  S.; Nenoff, Tina M.

doi:10.1021/acsami.0c02829

Luminescent Properties of DOBDC Containing MOFs: The Role of Free Hydroxyls

Journal Article · Mon Apr 27 00:00:00 EDT 2020 · ACS Applied Materials and Interfaces

DOI:https://doi.org/10.1021/acsami.0c02829· OSTI ID:1619220

^[1]; Rademacher, David ^[1]; ^[1]; Valdez, Nichole R. ^[1]; Rodriguez, Mark A. ^[1]; Rohwer, Lauren E. S. ^[1]; ^[1]

Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)

A novel metal–organic framework (MOF), Mn-DOBDC, has been synthesized in an effort to investigate the role of both the metal center and presence of free linker hydroxyls on the luminescent properties of DOBDC (2,5-dihydroxyterephthalic acid) containing MOFs. Co-MOF-74, RE-DOBDC (RE–Eu and Tb), and Mn-DOBDC have been synthesized and analyzed by powder X-ray diffraction (PXRD) and the fluorescent properties probed by UV–Vis spectroscopy and density functional theory (DFT). Mn-DOBDC has been synthesized by a new method involving a concurrent facile reflux synthesis and slow crystallization, resulting in yellow single crystals in monoclinic space group C2/c. Mn-DOBDC was further analyzed by single-crystal X-ray diffraction (SCXRD), scanning electron microscopy–energy-dispersive spectroscopy (SEM-EDS), and photoluminescent emission. Results indicate that the luminescent properties of the DOBDC linker are transferred to the three-dimensional structures of both the RE-DOBDC and Mn-DOBDC, which contain free hydroxyls on the linker. In Co-MOF-74 however, luminescence is quenched in the solid state due to binding of the phenolic hydroxyls within the MOF structure. Finally, Mn-DOBDC exhibits a ligand-based tunable emission that can be controlled in solution by the use of different solvents.

View Accepted Manuscript (DOE)

Research Organization:: Sandia National Laboratories (SNL-NM), Albuquerque, NM (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: AC04-94AL85000; SC0012577; NA0003525

OSTI ID:: 1619220

Report Number(s):: SAND--2020-1609J; 683701

Journal Information:: ACS Applied Materials and Interfaces, Journal Name: ACS Applied Materials and Interfaces Journal Issue: 20 Vol. 12; ISSN 1944-8244

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (51)

Luminescent Open Metal Sites within a Metal–Organic Framework for Sensing Small Molecules Chen, B.; Yang, Y.; Zapata, F. Advanced Materials, Vol. 19, Issue 13 https://doi.org/10.1002/adma.200601838	journal	July 2007
Metal–Organic Nanoporous Structures with Anisotropic Photoluminescence and Magnetic Properties and Their Use as Sensors Harbuzaru, Bogdan V.; Corma, Avelino; Rey, Fernando Angewandte Chemie International Edition, Vol. 47, Issue 6 https://doi.org/10.1002/anie.200704702	journal	January 2008
A Luminescent Metal-Organic Framework with Lewis Basic Pyridyl Sites for the Sensing of Metal Ions Chen, Banglin; Wang, Liangbo; Xiao, Yunqing Angewandte Chemie International Edition, Vol. 48, Issue 3 https://doi.org/10.1002/anie.200805101	journal	January 2009
Extraordinary NO ₂ Removal by the Metal-Organic Framework UiO-66-NH ₂ Peterson, Gregory W.; Mahle, John J.; DeCoste, Jared B. Angewandte Chemie International Edition, Vol. 55, Issue 21 https://doi.org/10.1002/anie.201601782	journal	April 2016
Base-Induced Formation of Two Magnesium Metal-Organic Framework Compounds with a Bifunctional Tetratopic Ligand Dietzel, Pascal D. C.; Blom, Richard; Fjellvåg, Helmer European Journal of Inorganic Chemistry, Vol. 2008, Issue 23 https://doi.org/10.1002/ejic.200701284	journal	August 2008
Semiempirical GGA-type density functional constructed with a long-range dispersion correction Grimme, Stefan Journal of Computational Chemistry, Vol. 27, Issue 15, p. 1787-1799 https://doi.org/10.1002/jcc.20495	journal	January 2006
Coordination Polymers Based on the 2,5-Dihydroxyterephthalate Ion and Alkaline Earth Metal (Ca, Sr) and Manganese Cations Dietzel, Pascal C.; Blom, Richard; Fjellvåg, Helmer Zeitschrift für anorganische und allgemeine Chemie, Vol. 635, Issue 12 https://doi.org/10.1002/zaac.200900348	journal	October 2009
Principles of Fluorescence Spectroscopy Lakowicz, Joseph R. Springer New York, NY https://doi.org/10.1007/978-0-387-46312-4	book	January 2006
Structural and electronic properties of M-MOF-74 (M = Mg, Co or Mn) de Oliveira, Aline; de Lima, Guilherme Ferreira; De Abreu, Heitor Avelino Chemical Physics Letters, Vol. 691 https://doi.org/10.1016/j.cplett.2017.11.027	journal	January 2018
The iron member of the CPO-27 coordination polymer series: Synthesis, characterization, and intriguing redox properties Märcz, Matthias; Johnsen, Rune E.; Dietzel, Pascal D. C. Microporous and Mesoporous Materials, Vol. 157 https://doi.org/10.1016/j.micromeso.2011.12.035	journal	July 2012
Luminescent transition metal–organic frameworks: An emerging sensor for detecting biologically essential metal ions Pamei, Mala; Puzari, Amrit Nano-Structures & Nano-Objects, Vol. 19 https://doi.org/10.1016/j.nanoso.2019.100364	journal	July 2019
First-Principles Treatment of Photoluminescence in Semiconductors Vogel, Dayton J.; Kilin, Dmitri S. The Journal of Physical Chemistry C, Vol. 119, Issue 50 https://doi.org/10.1021/acs.jpcc.5b06434	journal	December 2015
Defect and Linker Effects on the Binding of Organophosphorous Compounds in UiO-66 and Rare-Earth MOFs Harvey, Jacob A.; Greathouse, Jeffery A.; Sava Gallis, Dorina F. The Journal of Physical Chemistry C, Vol. 122, Issue 47 https://doi.org/10.1021/acs.jpcc.8b06198	journal	November 2018
Magnetic Tunability in RE-DOBDC MOFs via NO _x Acid Gas Adsorption Henkelis, Susan E.; Huber, Dale L.; Vogel, Dayton J. ACS Applied Materials & Interfaces, Vol. 12, Issue 17 https://doi.org/10.1021/acsami.0c01813	journal	April 2020
NO _x Adsorption and Optical Detection in Rare Earth Metal–Organic Frameworks Sava Gallis, Dorina F.; Vogel, Dayton J.; Vincent, Grace A. ACS Applied Materials & Interfaces, Vol. 11, Issue 46 https://doi.org/10.1021/acsami.9b16470	journal	October 2019
First-Principles Study of Microporous Magnets M-MOF-74 (M = Ni, Co, Fe, Mn): the Role of Metal Centers Zhang, Qiuju; Li, Baihai; Chen, Liang Inorganic Chemistry, Vol. 52, Issue 16 https://doi.org/10.1021/ic400927m	journal	August 2013
Infinite polymeric frameworks consisting of three dimensionally linked rod-like segments Hoskins, Bernard F.; Robson, Richard Journal of the American Chemical Society, Vol. 111, Issue 15 https://doi.org/10.1021/ja00197a079	journal	July 1989
Rod Packings and Metal−Organic Frameworks Constructed from Rod-Shaped Secondary Building Units Rosi, Nathaniel L.; Kim, Jaheon; Eddaoudi, Mohamed Journal of the American Chemical Society, Vol. 127, Issue 5, p. 1504-1518 https://doi.org/10.1021/ja045123o	journal	February 2005
Surface Modification and Functionalization of Nanoscale Metal-Organic Frameworks for Controlled Release and Luminescence Sensing Rieter, William J.; Taylor, Kathryn M. L.; Lin, Wenbin Journal of the American Chemical Society, Vol. 129, Issue 32 https://doi.org/10.1021/ja073506r	journal	August 2007
Exceptional Behavior over the Whole Adsorption−Storage−Delivery Cycle for NO in Porous Metal Organic Frameworks McKinlay, Alistair C.; Xiao, Bo; Wragg, David S. Journal of the American Chemical Society, Vol. 130, Issue 31 https://doi.org/10.1021/ja801997r	journal	August 2008
Fundamental Aspects of H ₂ S Adsorption on CPO-27-Ni Chavan, Sachin; Bonino, Francesca; Valenzano, Loredana The Journal of Physical Chemistry C, Vol. 117, Issue 30 https://doi.org/10.1021/jp402440u	journal	July 2013
Effect of Metal in M ₃ (btc) ₂ and M ₂ (dobdc) MOFs for O ₂ /N ₂ Separations: A Combined Density Functional Theory and Experimental Study Parkes, Marie V.; Sava Gallis, Dorina F.; Greathouse, Jeffery A. The Journal of Physical Chemistry C, Vol. 119, Issue 12 https://doi.org/10.1021/jp511789g	journal	March 2015
CO Adsorption on CPO-27-Ni Coordination Polymer: Spectroscopic Features and Interaction Energy Chavan, Sachin; Vitillo, Jenny G.; Groppo, Elena The Journal of Physical Chemistry C, Vol. 113, Issue 8 https://doi.org/10.1021/jp809872w	journal	January 2009
Interactions of NO ₂ with Zr-Based MOF: Effects of the Size of Organic Linkers on NO ₂ Adsorption at Ambient Conditions Ebrahim, Amani M.; Levasseur, Benoit; Bandosz, Teresa J. Langmuir, Vol. 29, Issue 1 https://doi.org/10.1021/la302869m	journal	December 2012
Ethene/Ethane and Propene/Propane Separation via the Olefin and Paraffin Selective Metal–Organic Framework Adsorbents CPO-27 and ZIF-8 Böhme, Ulrike; Barth, Benjamin; Paula, Carolin Langmuir, Vol. 29, Issue 27 https://doi.org/10.1021/la401471g	journal	June 2013
Comprehensive study of carbon dioxide adsorption in the metal–organic frameworks M ₂ (dobdc) (M = Mg, Mn, Fe, Co, Ni, Cu, Zn) Queen, Wendy L.; Hudson, Matthew R.; Bloch, Eric D. Chem. Sci., Vol. 5, Issue 12 https://doi.org/10.1039/C4SC02064B	journal	January 2014
Intriguing differences in hydrogen adsorption in CPO-27 materials induced by metal substitution Rosnes, Mali H.; Opitz, Martin; Frontzek, Matthias Journal of Materials Chemistry A, Vol. 3, Issue 9 https://doi.org/10.1039/C4TA05794E	journal	January 2015
Optimised room temperature, water-based synthesis of CPO-27-M metal–organic frameworks with high space-time yields Garzón-Tovar, L.; Carné-Sánchez, A.; Carbonell, C. Journal of Materials Chemistry A, Vol. 3, Issue 41 https://doi.org/10.1039/C5TA04923G	journal	January 2015
DFT insights into the adsorption of NH ₃ -SCR related small gases in Mn-MOF-74 Zhang, Minhua; Huang, Xuewei; Chen, Yifei Physical Chemistry Chemical Physics, Vol. 18, Issue 41 https://doi.org/10.1039/C6CP05557E	journal	January 2016
A luminescent metal organic framework with high sensitivity for detecting and removing copper ions from simulated biological fluids Zheng, Tian-Tian; Zhao, Jiao; Fang, Zhou-Wen Dalton Transactions, Vol. 46, Issue 8 https://doi.org/10.1039/C6DT04630D	journal	January 2017
Low temperature synthesis study of metal–organic framework CPO-27: investigating metal, solvent and base effects down to −78 °C Vornholt, Simon M.; Henkelis, Susan E.; Morris, Russell E. Dalton Transactions, Vol. 46, Issue 25 https://doi.org/10.1039/C7DT01223C	journal	January 2017
Structural characterization of framework–gas interactions in the metal–organic framework Co ₂ (dobdc) by in situ single-crystal X-ray diffraction Gonzalez, Miguel I.; Mason, Jarad A.; Bloch, Eric D. Chemical Science, Vol. 8, Issue 6 https://doi.org/10.1039/C7SC00449D	journal	January 2017
A single crystal study of CPO-27 and UTSA-74 for nitric oxide storage and release Henkelis, Susan E.; Vornholt, Simon M.; Cordes, David B. CrystEngComm, Vol. 21, Issue 12 https://doi.org/10.1039/C9CE00098D	journal	January 2019
Structure and electronic properties of rare earth DOBDC metal–organic-frameworks Vogel, Dayton J.; Sava Gallis, Dorina F.; Nenoff, Tina M. Physical Chemistry Chemical Physics, Vol. 21, Issue 41 https://doi.org/10.1039/C9CP04038B	journal	January 2019
A highly crystalline anthracene-based MOF-74 series featuring electrical conductivity and luminescence Scheurle, Patricia I.; Mähringer, Andre; Jakowetz, Andreas C. Nanoscale, Vol. 11, Issue 43 https://doi.org/10.1039/C9NR05431F	journal	January 2019
Hydrogen adsorption in a nickel based coordination polymer with open metal sites in the cylindrical cavities of the desolvated framework Dietzel, Pascal D. C.; Panella, Barbara; Hirscher, Michael Chemical Communications, Issue 9 https://doi.org/10.1039/b515434k	journal	January 2006
Response of CPO-27-Ni towards CO, N2 and C2H4 Chavan, Sachin; Bonino, Francesca; Vitillo, Jenny G. Physical Chemistry Chemical Physics, Vol. 11, Issue 42 https://doi.org/10.1039/b907258f	journal	January 2009
Tunable emission from a porous metal–organic framework by employing an excited-state intramolecular proton transfer responsive ligand Jayaramulu, K.; Kanoo, Prakash; George, Subi J. Chemical Communications, Vol. 46, Issue 42 https://doi.org/10.1039/c0cc02069a	journal	January 2010
A luminescent nanoscale metal–organic framework for sensing of nitroaromatic explosives Xu, Hui; Liu, Fu; Cui, Yuanjing Chemical Communications, Vol. 47, Issue 11 https://doi.org/10.1039/c0cc05166g	journal	January 2011
First-principles Hubbard U approach for small molecule binding in metal-organic frameworks Mann, Gregory W.; Lee, Kyuho; Cococcioni, Matteo The Journal of Chemical Physics, Vol. 144, Issue 17 https://doi.org/10.1063/1.4947240	journal	May 2016
Crystal Structures, Topological Analyses, and Magnetic Properties of Manganese-Dihydroxyterephthalate Complexes Gao, Qiang; Jiang, Fei-Long; Wu, Ming-Yan Australian Journal of Chemistry, Vol. 63, Issue 2 https://doi.org/10.1071/CH09378	journal	January 2010
Ab initiomolecular dynamics for liquid metals Kresse, G.; Hafner, J. Physical Review B, Vol. 47, Issue 1, p. 558-561 https://doi.org/10.1103/PhysRevB.47.558	journal	January 1993
Ab initio molecular-dynamics simulation of the liquid-metal–amorphous-semiconductor transition in germanium Kresse, G.; Hafner, J. Physical Review B, Vol. 49, Issue 20, p. 14251-14269 https://doi.org/10.1103/PhysRevB.49.14251	journal	May 1994
Projector augmented-wave method Blöchl, P. E. Physical Review B, Vol. 50, Issue 24, p. 17953-17979 https://doi.org/10.1103/PhysRevB.50.17953	journal	December 1994
From ultrasoft pseudopotentials to the projector augmented-wave method Kresse, G.; Joubert, D. Physical Review B, Vol. 59, Issue 3, p. 1758-1775 https://doi.org/10.1103/PhysRevB.59.1758	journal	January 1999
Generalized Gradient Approximation Made Simple Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868 https://doi.org/10.1103/PhysRevLett.77.3865	journal	October 1996
Generalized Gradient Approximation Made Simple [Phys. Rev. Lett. 77, 3865 (1996)] Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias Physical Review Letters, Vol. 78, Issue 7 https://doi.org/10.1103/PhysRevLett.78.1396	journal	February 1997
OLEX2 : a complete structure solution, refinement and analysis program Dolomanov, Oleg V.; Bourhis, Luc J.; Gildea, Richard J. Journal of Applied Crystallography, Vol. 42, Issue 2 https://doi.org/10.1107/S0021889808042726	journal	January 2009
Crystal structure refinement with SHELXL Sheldrick, George M. Acta Crystallographica Section C Structural Chemistry, Vol. 71, Issue 1, p. 3-8 https://doi.org/10.1107/S2053229614024218	journal	January 2015
SHELXT – Integrated space-group and crystal-structure determination Sheldrick, George M. Acta Crystallographica Section A Foundations and Advances, Vol. 71, Issue 1, p. 3-8 https://doi.org/10.1107/S2053273314026370	journal	January 2015
Systematic Design of Pore Size and Functionality in Isoreticular MOFs and Their Application in Methane Storage Eddaoudi, Mohamed; Kim, Jaheon; Rosi, Nathaniel Science, Vol. 295, Issue 5554, p. 469-472 https://doi.org/10.1126/science.1067208	journal	January 2002

Similar Records

Magnetic Tunability in RE-DOBDC MOFs via NO_x Acid Gas Adsorption

Journal Article · Mon Apr 06 00:00:00 EDT 2020 · ACS Applied Materials and Interfaces · OSTI ID:1619219

Structurally Driven Selective Adsorption of Hydrocarbons by Metal Substitution in Isostructural Rare-Earth Metal–Organic Frameworks

Journal Article · Wed Mar 05 23:00:00 EST 2025 · Industrial and Engineering Chemistry Research · OSTI ID:2563816

Tuned Hydrogen Bonding in Rare-Earth Metal–Organic Frameworks for Design of Optical and Electronic Properties: An Exemplar Study of Y–2,5-Dihydroxyterephthalic Acid

Journal Article · Sun Jan 05 23:00:00 EST 2020 · ACS Applied Materials and Interfaces · OSTI ID:1601266

Related Subjects

36 MATERIALS SCIENCE
MOF
luminescence
metal-organic framework

Luminescent Properties of DOBDC Containing MOFs: The Role of Free Hydroxyls

Citation Formats

References (51)

Linked Research (1)

Similar Records

Related Subjects