Permanent Porosity in the Room-Temperature Magnet and Magnonic Material V(TCNE)2

Jesse G. Park; David E. Jaramillo; Yueguang Shi; Henry Z.H. Jiang; Huma Yusuf; Hiroyasu Furukawa; Eric D. Bloch; Donley S. Cormode; Joel S. Miller; T. David Harris; Ezekiel Johnston-Halperin; Michael E. Flatté; Jeffrey R. Long

doi:10.1021/acscentsci.3c00053

Permanent Porosity in the Room-Temperature Magnet and Magnonic Material V(TCNE)₂

Jesse G. Park
, David E. Jaramillo
, Yueguang Shi
, Henry Z.H. Jiang
, Huma Yusuf
, Hiroyasu Furukawa
, Eric D. Bloch
, Donley S. Cormode
, Joel S. Miller
, T. David Harris
, Ezekiel Johnston-Halperin
, Michael E. Flatté
, Jeffrey R. Long (Corresponding author)

Research output: Contribution to journal › Article › Academic › peer-review

15 Citations (Scopus)

151 Downloads (Pure)

Abstract

Materials that simultaneously exhibit permanent porosity and high-temperature magnetic order could lead to advances in fundamental physics and numerous emerging technologies. Herein, we show that the archetypal molecule-based magnet and magnonic material V(TCNE)₂ (TCNE = tetracyanoethylene) can be desolvated to generate a room-temperature microporous magnet. The solution-phase reaction of V(CO)₆ with TCNE yields V(TCNE)₂·0.95CH₂Cl₂, for which a characteristic temperature of T* = 646 K is estimated from a Bloch fit to variable-temperature magnetization data. Removal of the solvent under reduced pressure affords the activated compound V(TCNE)₂, which exhibits a T* value of 590 K and permanent microporosity (Langmuir surface area of 850 m²/g). The porous structure of V(TCNE)₂ is accessible to the small gas molecules H₂, N₂, O₂, CO₂, ethane, and ethylene. While V(TCNE)₂ exhibits thermally activated electron transfer with O₂, all the other studied gases engage in physisorption. The T* value of V(TCNE)₂ is slightly modulated upon adsorption of H₂ (T* = 583 K) or CO₂ (T* = 596 K), while it decreases more significantly upon ethylene insertion (T* = 459 K). These results provide an initial demonstration of microporosity in a room-temperature magnet and highlight the possibility of further incorporation of small-molecule guests, potentially even molecular qubits, toward future applications.

Original language	English
Pages (from-to)	777-786
Number of pages	10
Journal	ACS Central Science
Volume	9
Issue number	4
DOIs	https://doi.org/10.1021/acscentsci.3c00053
Publication status	Published - 26 Apr 2023

Bibliographical note

Funding Information:
This research was supported as part of the Center for Molecular Quantum Transduction (CMQT), an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences, under Award No. DE-SC0021314. We thank the National Science Foundation Graduate Research Fellowship Program for providing support for J.G.P. and D.E.J. In addition, we thank Ryan A. Murphy for helpful discussions and experimental assistance, Dr. Lucy E. Darago, Kennedy McCone, and Dr. Rodolfo M. Torres-Gavosto for experimental assistance, and Dr. Katie R. Meihaus for editorial assistance.

Funding

This research was supported as part of the Center for Molecular Quantum Transduction (CMQT), an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences, under Award No. DE-SC0021314. We thank the National Science Foundation Graduate Research Fellowship Program for providing support for J.G.P. and D.E.J. In addition, we thank Ryan A. Murphy for helpful discussions and experimental assistance, Dr. Lucy E. Darago, Kennedy McCone, and Dr. Rodolfo M. Torres-Gavosto for experimental assistance, and Dr. Katie R. Meihaus for editorial assistance.

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Cite this

@article{83245bd5c0e2476a814c3264892b30a0,

title = "Permanent Porosity in the Room-Temperature Magnet and Magnonic Material V(TCNE)2",

abstract = "Materials that simultaneously exhibit permanent porosity and high-temperature magnetic order could lead to advances in fundamental physics and numerous emerging technologies. Herein, we show that the archetypal molecule-based magnet and magnonic material V(TCNE)2 (TCNE = tetracyanoethylene) can be desolvated to generate a room-temperature microporous magnet. The solution-phase reaction of V(CO)6 with TCNE yields V(TCNE)2·0.95CH2Cl2, for which a characteristic temperature of T* = 646 K is estimated from a Bloch fit to variable-temperature magnetization data. Removal of the solvent under reduced pressure affords the activated compound V(TCNE)2, which exhibits a T* value of 590 K and permanent microporosity (Langmuir surface area of 850 m2/g). The porous structure of V(TCNE)2 is accessible to the small gas molecules H2, N2, O2, CO2, ethane, and ethylene. While V(TCNE)2 exhibits thermally activated electron transfer with O2, all the other studied gases engage in physisorption. The T* value of V(TCNE)2 is slightly modulated upon adsorption of H2 (T* = 583 K) or CO2 (T* = 596 K), while it decreases more significantly upon ethylene insertion (T* = 459 K). These results provide an initial demonstration of microporosity in a room-temperature magnet and highlight the possibility of further incorporation of small-molecule guests, potentially even molecular qubits, toward future applications.",

author = "Park, \{Jesse G.\} and Jaramillo, \{David E.\} and Yueguang Shi and Jiang, \{Henry Z.H.\} and Huma Yusuf and Hiroyasu Furukawa and Bloch, \{Eric D.\} and Cormode, \{Donley S.\} and Miller, \{Joel S.\} and Harris, \{T. David\} and Ezekiel Johnston-Halperin and Flatt{\'e}, \{Michael E.\} and Long, \{Jeffrey R.\}",

note = "Funding Information: This research was supported as part of the Center for Molecular Quantum Transduction (CMQT), an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences, under Award No. DE-SC0021314. We thank the National Science Foundation Graduate Research Fellowship Program for providing support for J.G.P. and D.E.J. In addition, we thank Ryan A. Murphy for helpful discussions and experimental assistance, Dr. Lucy E. Darago, Kennedy McCone, and Dr. Rodolfo M. Torres-Gavosto for experimental assistance, and Dr. Katie R. Meihaus for editorial assistance. ",

year = "2023",

month = apr,

day = "26",

doi = "10.1021/acscentsci.3c00053",

language = "English",

volume = "9",

pages = "777--786",

journal = "ACS Central Science",

issn = "2374-7943",

publisher = "American Chemical Society",

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TY - JOUR

T1 - Permanent Porosity in the Room-Temperature Magnet and Magnonic Material V(TCNE)2

AU - Park, Jesse G.

AU - Jaramillo, David E.

AU - Shi, Yueguang

AU - Jiang, Henry Z.H.

AU - Yusuf, Huma

AU - Furukawa, Hiroyasu

AU - Bloch, Eric D.

AU - Cormode, Donley S.

AU - Miller, Joel S.

AU - Harris, T. David

AU - Johnston-Halperin, Ezekiel

AU - Flatté, Michael E.

AU - Long, Jeffrey R.

N1 - Funding Information: This research was supported as part of the Center for Molecular Quantum Transduction (CMQT), an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences, under Award No. DE-SC0021314. We thank the National Science Foundation Graduate Research Fellowship Program for providing support for J.G.P. and D.E.J. In addition, we thank Ryan A. Murphy for helpful discussions and experimental assistance, Dr. Lucy E. Darago, Kennedy McCone, and Dr. Rodolfo M. Torres-Gavosto for experimental assistance, and Dr. Katie R. Meihaus for editorial assistance.

PY - 2023/4/26

Y1 - 2023/4/26

N2 - Materials that simultaneously exhibit permanent porosity and high-temperature magnetic order could lead to advances in fundamental physics and numerous emerging technologies. Herein, we show that the archetypal molecule-based magnet and magnonic material V(TCNE)2 (TCNE = tetracyanoethylene) can be desolvated to generate a room-temperature microporous magnet. The solution-phase reaction of V(CO)6 with TCNE yields V(TCNE)2·0.95CH2Cl2, for which a characteristic temperature of T* = 646 K is estimated from a Bloch fit to variable-temperature magnetization data. Removal of the solvent under reduced pressure affords the activated compound V(TCNE)2, which exhibits a T* value of 590 K and permanent microporosity (Langmuir surface area of 850 m2/g). The porous structure of V(TCNE)2 is accessible to the small gas molecules H2, N2, O2, CO2, ethane, and ethylene. While V(TCNE)2 exhibits thermally activated electron transfer with O2, all the other studied gases engage in physisorption. The T* value of V(TCNE)2 is slightly modulated upon adsorption of H2 (T* = 583 K) or CO2 (T* = 596 K), while it decreases more significantly upon ethylene insertion (T* = 459 K). These results provide an initial demonstration of microporosity in a room-temperature magnet and highlight the possibility of further incorporation of small-molecule guests, potentially even molecular qubits, toward future applications.

AB - Materials that simultaneously exhibit permanent porosity and high-temperature magnetic order could lead to advances in fundamental physics and numerous emerging technologies. Herein, we show that the archetypal molecule-based magnet and magnonic material V(TCNE)2 (TCNE = tetracyanoethylene) can be desolvated to generate a room-temperature microporous magnet. The solution-phase reaction of V(CO)6 with TCNE yields V(TCNE)2·0.95CH2Cl2, for which a characteristic temperature of T* = 646 K is estimated from a Bloch fit to variable-temperature magnetization data. Removal of the solvent under reduced pressure affords the activated compound V(TCNE)2, which exhibits a T* value of 590 K and permanent microporosity (Langmuir surface area of 850 m2/g). The porous structure of V(TCNE)2 is accessible to the small gas molecules H2, N2, O2, CO2, ethane, and ethylene. While V(TCNE)2 exhibits thermally activated electron transfer with O2, all the other studied gases engage in physisorption. The T* value of V(TCNE)2 is slightly modulated upon adsorption of H2 (T* = 583 K) or CO2 (T* = 596 K), while it decreases more significantly upon ethylene insertion (T* = 459 K). These results provide an initial demonstration of microporosity in a room-temperature magnet and highlight the possibility of further incorporation of small-molecule guests, potentially even molecular qubits, toward future applications.

UR - https://www.scopus.com/pages/publications/85151354214

U2 - 10.1021/acscentsci.3c00053

DO - 10.1021/acscentsci.3c00053

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