Synthesis, Characterization, and Thermal Properties of N -alkyl β-Diketiminate Manganese Complexes

Madelyn M. Stalzer; Tracy L. Lohr; Tobin J. Marks

doi:10.1021/acs.inorgchem.7b02476

Synthesis, Characterization, and Thermal Properties of N -alkyl β-Diketiminate Manganese Complexes

Madelyn M. Stalzer, Tracy L. Lohr^*, Tobin J. Marks

^*Corresponding author for this work

Chemistry

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

21 Scopus citations

Abstract

A series of N,N′-dialkyl-β-diketiminato manganese(II) complexes was synthesized and characterized by single crystal X-ray diffraction, UV-vis and FTIR spectroscopy, and then assayed for volatility, thermal stability, and surface reactivity relevant to vapor-phase film growth processes. Bis(N,N′-dimethyl-4-amino-3-penten-2-imine) manganese(II), 1, and bis(N-N′-diisopropyl-4-amino-3-penten-2-imine) manganese(II), 2, specifically, emerge as the most promising candidates, balancing volatility (sublimation temperatures < 100 °C at 100 mTorr) with coordinative unsaturation and reactivity, as revealed by rapid release of ligand in the presence of a silica surface. Good correlation is observed between buried volume calculations and relative surface reactivity data, indicating that metal availability resulting from sterically open ligand alkyl substituents increases surface reactivity. The thermal stability, volatility, and reactivity exhibited by these compounds render them promising precursors for the growth of manganese oxide films via vapor-phase growth processes.

Original language	English (US)
Pages (from-to)	3017-3024
Number of pages	8
Journal	Inorganic chemistry
Volume	57
Issue number	6
DOIs	https://doi.org/10.1021/acs.inorgchem.7b02476
State	Published - Mar 19 2018

Funding

This work was supported as part of the Center for Electrochemical Energy Science, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences (Award No. DE-AC02-06CH11357). This work made use of the Keck-II facility of Northwestern University's NUANCE Center, which has received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-1542205); the MRSEC program (NSF DMR-1121262) at the Materials Research Center; the International Institute for Nanotechnology (IIN); the Keck Foundation; and the State of Illinois, through the IIN. This work also made use of the IMSERC at Northwestern University which has received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF NNCI-1542205); the State of Illinois and International Institute for Nanotechnology (IIN); and the NSF (NSF CHE-9871268).

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry

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10.1021/acs.inorgchem.7b02476

Cite this

@article{9d09bdce66ba4dda8ac1bbf7d9eeff9b,

title = "Synthesis, Characterization, and Thermal Properties of N -alkyl β-Diketiminate Manganese Complexes",

abstract = "A series of N,N′-dialkyl-β-diketiminato manganese(II) complexes was synthesized and characterized by single crystal X-ray diffraction, UV-vis and FTIR spectroscopy, and then assayed for volatility, thermal stability, and surface reactivity relevant to vapor-phase film growth processes. Bis(N,N′-dimethyl-4-amino-3-penten-2-imine) manganese(II), 1, and bis(N-N′-diisopropyl-4-amino-3-penten-2-imine) manganese(II), 2, specifically, emerge as the most promising candidates, balancing volatility (sublimation temperatures < 100 °C at 100 mTorr) with coordinative unsaturation and reactivity, as revealed by rapid release of ligand in the presence of a silica surface. Good correlation is observed between buried volume calculations and relative surface reactivity data, indicating that metal availability resulting from sterically open ligand alkyl substituents increases surface reactivity. The thermal stability, volatility, and reactivity exhibited by these compounds render them promising precursors for the growth of manganese oxide films via vapor-phase growth processes.",

author = "Stalzer, {Madelyn M.} and Lohr, {Tracy L.} and Marks, {Tobin J.}",

note = "Funding Information: This work was supported as part of the Center for Electrochemical Energy Science, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences (Award No. DE-AC02-06CH11357). This work made use of the Keck-II facility of Northwestern University's NUANCE Center, which has received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-1542205); the MRSEC program (NSF DMR-1121262) at the Materials Research Center; the International Institute for Nanotechnology (IIN); the Keck Foundation; and the State of Illinois, through the IIN. This work also made use of the IMSERC at Northwestern University which has received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF NNCI-1542205); the State of Illinois and International Institute for Nanotechnology (IIN); and the NSF (NSF CHE-9871268). Publisher Copyright: {\textcopyright} 2018 American Chemical Society.",

year = "2018",

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doi = "10.1021/acs.inorgchem.7b02476",

language = "English (US)",

volume = "57",

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journal = "Inorganic chemistry",

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T1 - Synthesis, Characterization, and Thermal Properties of N -alkyl β-Diketiminate Manganese Complexes

AU - Stalzer, Madelyn M.

AU - Lohr, Tracy L.

AU - Marks, Tobin J.

N1 - Funding Information: This work was supported as part of the Center for Electrochemical Energy Science, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences (Award No. DE-AC02-06CH11357). This work made use of the Keck-II facility of Northwestern University's NUANCE Center, which has received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-1542205); the MRSEC program (NSF DMR-1121262) at the Materials Research Center; the International Institute for Nanotechnology (IIN); the Keck Foundation; and the State of Illinois, through the IIN. This work also made use of the IMSERC at Northwestern University which has received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF NNCI-1542205); the State of Illinois and International Institute for Nanotechnology (IIN); and the NSF (NSF CHE-9871268). Publisher Copyright: © 2018 American Chemical Society.

PY - 2018/3/19

Y1 - 2018/3/19

N2 - A series of N,N′-dialkyl-β-diketiminato manganese(II) complexes was synthesized and characterized by single crystal X-ray diffraction, UV-vis and FTIR spectroscopy, and then assayed for volatility, thermal stability, and surface reactivity relevant to vapor-phase film growth processes. Bis(N,N′-dimethyl-4-amino-3-penten-2-imine) manganese(II), 1, and bis(N-N′-diisopropyl-4-amino-3-penten-2-imine) manganese(II), 2, specifically, emerge as the most promising candidates, balancing volatility (sublimation temperatures < 100 °C at 100 mTorr) with coordinative unsaturation and reactivity, as revealed by rapid release of ligand in the presence of a silica surface. Good correlation is observed between buried volume calculations and relative surface reactivity data, indicating that metal availability resulting from sterically open ligand alkyl substituents increases surface reactivity. The thermal stability, volatility, and reactivity exhibited by these compounds render them promising precursors for the growth of manganese oxide films via vapor-phase growth processes.

AB - A series of N,N′-dialkyl-β-diketiminato manganese(II) complexes was synthesized and characterized by single crystal X-ray diffraction, UV-vis and FTIR spectroscopy, and then assayed for volatility, thermal stability, and surface reactivity relevant to vapor-phase film growth processes. Bis(N,N′-dimethyl-4-amino-3-penten-2-imine) manganese(II), 1, and bis(N-N′-diisopropyl-4-amino-3-penten-2-imine) manganese(II), 2, specifically, emerge as the most promising candidates, balancing volatility (sublimation temperatures < 100 °C at 100 mTorr) with coordinative unsaturation and reactivity, as revealed by rapid release of ligand in the presence of a silica surface. Good correlation is observed between buried volume calculations and relative surface reactivity data, indicating that metal availability resulting from sterically open ligand alkyl substituents increases surface reactivity. The thermal stability, volatility, and reactivity exhibited by these compounds render them promising precursors for the growth of manganese oxide films via vapor-phase growth processes.

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JO - Inorganic chemistry

JF - Inorganic chemistry

IS - 6

ER -

Synthesis, Characterization, and Thermal Properties of N -alkyl β-Diketiminate Manganese Complexes

Abstract

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ASJC Scopus subject areas

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CCDC 1576501: Experimental Crystal Structure Determination

CCDC 1576504: Experimental Crystal Structure Determination

CCDC 1576502: Experimental Crystal Structure Determination

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Synthesis, Characterization, and Thermal Properties of N -alkyl β-Diketiminate Manganese Complexes

Abstract

Funding

ASJC Scopus subject areas

Access to Document

Other files and links

Fingerprint

Datasets

CCDC 1576501: Experimental Crystal Structure Determination

CCDC 1576504: Experimental Crystal Structure Determination

CCDC 1576502: Experimental Crystal Structure Determination

Cite this