Influence of Rare-Earth Ion Radius on Metal-Metal Charge Transfer in Trinuclear Mixed-Valent Complexes

Cole Carter; Yosi Kratish; Tobin J. Marks

doi:10.1021/acs.inorgchem.2c03973

Influence of Rare-Earth Ion Radius on Metal-Metal Charge Transfer in Trinuclear Mixed-Valent Complexes

Cole Carter, Yosi Kratish^*, Tobin J. Marks^*

^*Corresponding author for this work

Chemistry

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

3 Scopus citations

Abstract

We report the synthesis and characterization of a highly conjugated bisferrocenyl pyrrolediimine ligand, Fc₂PyrDIH (1), and its trinuclear complexes with rare earth ions─(Fc₂PyrDI)M(N(TMS)₂)₂ (2-M, M = Sc, Y, Lu, La). Crystal structures, nuclear magnetic resonance (NMR) spectra, and ultraviolet/visible/near-infrared (UV/vis-NIR) data are presented. The latter are in good agreement with DFT calculations, illuminating the impact of the rare earth ionic radius on NIR charge transfer excitations. For [2-Sc]⁺, the charge transfer is at 11,500 cm^-1, while for [2-Y]⁺, only a d-d transition at 8000 cm^-1 is observed. Lu has an ionic radius in between Sc and Y, and the [2-Lu]⁺ complex exhibits both transitions. From time-dependent density functional theory (TDDFT) analysis, we assign the 11,500 cm^-1 transition as a mixture of metal-to-ligand charge transfer (MLCT) and metal-to-metal charge transfer (MMCT), rather than pure metal-to-metal CT because it has significant ligand character. Typically, the ferrocenes moieties have high rotational freedom in bis-ferrocenyl mixed valent complexes. However, in the present (Fc₂PyrDI)M(N(TMS)₂)₂ complexes, ligand-ligand repulsions lock the rotational freedom so that rare-earth ionic radius-dependent geometric differences increasingly influence orbital overlap as the ionic radius falls.

Original language	English (US)
Pages (from-to)	4799-4813
Number of pages	15
Journal	Inorganic chemistry
Volume	62
Issue number	12
DOIs	https://doi.org/10.1021/acs.inorgchem.2c03973
State	Published - Mar 27 2023

Funding

Financial support was provided by the National Science Foundation through the CHE-CAT program, Grant No. CHE-1856619 (C.C.). Financial support by the Office of Basic Energy Sciences, Department of Energy (DE-FG02-03ER15457) to the Institute for Catalysis in Energy Processes (ICEP) at Northwestern University (Y.K.) is gratefully acknowledged. This work used the IMSERC facility at Northwestern University, which has received support from the NSF (CHE-1048773 and CHE-9871268); Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF NNCI-1542205); the State of Illinois and International Institute for Nanotechnology. In addition, this work made use of the GIANTFab core facility at Northwestern University. GIANTFab is supported by the Institute for Sustainability and Energy at Northwestern and the Office of the Vice President for Research at Northwestern. We also thank Dr. N. La Porte for assistance in specEchem measurements, as well as Dr. Charlolette Stern for refining the crystal structure for 4-La and 3-Y .

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry

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10.1021/acs.inorgchem.2c03973

Cite this

@article{5ec1d9f2ab204cffb9663fb01b9cdde1,

title = "Influence of Rare-Earth Ion Radius on Metal-Metal Charge Transfer in Trinuclear Mixed-Valent Complexes",

abstract = "We report the synthesis and characterization of a highly conjugated bisferrocenyl pyrrolediimine ligand, Fc2PyrDIH (1), and its trinuclear complexes with rare earth ions─(Fc2PyrDI)M(N(TMS)2)2 (2-M, M = Sc, Y, Lu, La). Crystal structures, nuclear magnetic resonance (NMR) spectra, and ultraviolet/visible/near-infrared (UV/vis-NIR) data are presented. The latter are in good agreement with DFT calculations, illuminating the impact of the rare earth ionic radius on NIR charge transfer excitations. For [2-Sc]+, the charge transfer is at 11,500 cm-1, while for [2-Y]+, only a d-d transition at 8000 cm-1 is observed. Lu has an ionic radius in between Sc and Y, and the [2-Lu]+ complex exhibits both transitions. From time-dependent density functional theory (TDDFT) analysis, we assign the 11,500 cm-1 transition as a mixture of metal-to-ligand charge transfer (MLCT) and metal-to-metal charge transfer (MMCT), rather than pure metal-to-metal CT because it has significant ligand character. Typically, the ferrocenes moieties have high rotational freedom in bis-ferrocenyl mixed valent complexes. However, in the present (Fc2PyrDI)M(N(TMS)2)2 complexes, ligand-ligand repulsions lock the rotational freedom so that rare-earth ionic radius-dependent geometric differences increasingly influence orbital overlap as the ionic radius falls.",

author = "Cole Carter and Yosi Kratish and Marks, {Tobin J.}",

note = "Funding Information: Financial support was provided by the National Science Foundation through the CHE-CAT program, Grant No. CHE-1856619 (C.C.). Financial support by the Office of Basic Energy Sciences, Department of Energy (DE-FG02-03ER15457) to the Institute for Catalysis in Energy Processes (ICEP) at Northwestern University (Y.K.) is gratefully acknowledged. This work used the IMSERC facility at Northwestern University, which has received support from the NSF (CHE-1048773 and CHE-9871268); Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF NNCI-1542205); the State of Illinois and International Institute for Nanotechnology. In addition, this work made use of the GIANTFab core facility at Northwestern University. GIANTFab is supported by the Institute for Sustainability and Energy at Northwestern and the Office of the Vice President for Research at Northwestern. We also thank Dr. N. La Porte for assistance in specEchem measurements, as well as Dr. Charlolette Stern for refining the crystal structure for 4-La and 3-Y . Publisher Copyright: {\textcopyright} 2023 American Chemical Society.",

year = "2023",

month = mar,

day = "27",

doi = "10.1021/acs.inorgchem.2c03973",

language = "English (US)",

volume = "62",

pages = "4799--4813",

journal = "Inorganic chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "12",

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TY - JOUR

T1 - Influence of Rare-Earth Ion Radius on Metal-Metal Charge Transfer in Trinuclear Mixed-Valent Complexes

AU - Carter, Cole

AU - Kratish, Yosi

AU - Marks, Tobin J.

N1 - Funding Information: Financial support was provided by the National Science Foundation through the CHE-CAT program, Grant No. CHE-1856619 (C.C.). Financial support by the Office of Basic Energy Sciences, Department of Energy (DE-FG02-03ER15457) to the Institute for Catalysis in Energy Processes (ICEP) at Northwestern University (Y.K.) is gratefully acknowledged. This work used the IMSERC facility at Northwestern University, which has received support from the NSF (CHE-1048773 and CHE-9871268); Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF NNCI-1542205); the State of Illinois and International Institute for Nanotechnology. In addition, this work made use of the GIANTFab core facility at Northwestern University. GIANTFab is supported by the Institute for Sustainability and Energy at Northwestern and the Office of the Vice President for Research at Northwestern. We also thank Dr. N. La Porte for assistance in specEchem measurements, as well as Dr. Charlolette Stern for refining the crystal structure for 4-La and 3-Y . Publisher Copyright: © 2023 American Chemical Society.

PY - 2023/3/27

Y1 - 2023/3/27

N2 - We report the synthesis and characterization of a highly conjugated bisferrocenyl pyrrolediimine ligand, Fc2PyrDIH (1), and its trinuclear complexes with rare earth ions─(Fc2PyrDI)M(N(TMS)2)2 (2-M, M = Sc, Y, Lu, La). Crystal structures, nuclear magnetic resonance (NMR) spectra, and ultraviolet/visible/near-infrared (UV/vis-NIR) data are presented. The latter are in good agreement with DFT calculations, illuminating the impact of the rare earth ionic radius on NIR charge transfer excitations. For [2-Sc]+, the charge transfer is at 11,500 cm-1, while for [2-Y]+, only a d-d transition at 8000 cm-1 is observed. Lu has an ionic radius in between Sc and Y, and the [2-Lu]+ complex exhibits both transitions. From time-dependent density functional theory (TDDFT) analysis, we assign the 11,500 cm-1 transition as a mixture of metal-to-ligand charge transfer (MLCT) and metal-to-metal charge transfer (MMCT), rather than pure metal-to-metal CT because it has significant ligand character. Typically, the ferrocenes moieties have high rotational freedom in bis-ferrocenyl mixed valent complexes. However, in the present (Fc2PyrDI)M(N(TMS)2)2 complexes, ligand-ligand repulsions lock the rotational freedom so that rare-earth ionic radius-dependent geometric differences increasingly influence orbital overlap as the ionic radius falls.

AB - We report the synthesis and characterization of a highly conjugated bisferrocenyl pyrrolediimine ligand, Fc2PyrDIH (1), and its trinuclear complexes with rare earth ions─(Fc2PyrDI)M(N(TMS)2)2 (2-M, M = Sc, Y, Lu, La). Crystal structures, nuclear magnetic resonance (NMR) spectra, and ultraviolet/visible/near-infrared (UV/vis-NIR) data are presented. The latter are in good agreement with DFT calculations, illuminating the impact of the rare earth ionic radius on NIR charge transfer excitations. For [2-Sc]+, the charge transfer is at 11,500 cm-1, while for [2-Y]+, only a d-d transition at 8000 cm-1 is observed. Lu has an ionic radius in between Sc and Y, and the [2-Lu]+ complex exhibits both transitions. From time-dependent density functional theory (TDDFT) analysis, we assign the 11,500 cm-1 transition as a mixture of metal-to-ligand charge transfer (MLCT) and metal-to-metal charge transfer (MMCT), rather than pure metal-to-metal CT because it has significant ligand character. Typically, the ferrocenes moieties have high rotational freedom in bis-ferrocenyl mixed valent complexes. However, in the present (Fc2PyrDI)M(N(TMS)2)2 complexes, ligand-ligand repulsions lock the rotational freedom so that rare-earth ionic radius-dependent geometric differences increasingly influence orbital overlap as the ionic radius falls.

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U2 - 10.1021/acs.inorgchem.2c03973

DO - 10.1021/acs.inorgchem.2c03973

M3 - Article

C2 - 36921086

AN - SCOPUS:85150354826

SN - 0020-1669

VL - 62

SP - 4799

EP - 4813

JO - Inorganic chemistry

JF - Inorganic chemistry

IS - 12

ER -

Influence of Rare-Earth Ion Radius on Metal-Metal Charge Transfer in Trinuclear Mixed-Valent Complexes

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CCDC 2218384: Experimental Crystal Structure Determination

CCDC 2217096: Experimental Crystal Structure Determination

CCDC 2217097: Experimental Crystal Structure Determination

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Influence of Rare-Earth Ion Radius on Metal-Metal Charge Transfer in Trinuclear Mixed-Valent Complexes

Abstract

Funding

ASJC Scopus subject areas

Access to Document

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Datasets

CCDC 2218384: Experimental Crystal Structure Determination

CCDC 2217096: Experimental Crystal Structure Determination

CCDC 2217097: Experimental Crystal Structure Determination

Cite this