Pressure-Induced Spin-State Interconversion of [Fe(6-Me-py)3tren](ClO4)2 in Solution

William S. Hammack; Andrew J. Conti; David N. Hendrickson; Harry G. Drickamer

doi:10.1021/ja00187a027

Pressure-Induced Spin-State Interconversion of [Fe(6-Me-py)₃tren](ClO₄)₂ in Solution

William S. Hammack, Andrew J. Conti, David N. Hendrickson, Harry G. Drickamer

Chemical and Biomolecular Engineering

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

Abstract

The series of pseudooctahedral Fe^II spin-crossover complexes [Fe(6-Me-py)₃tren](ClO₄)₂(4), [Fe(6-Me- py)₂Pytren](ClO₄)₂(3), and [Fe(6-Me-py)py₂tren](ClO₄)₂(2) exhibit varying degrees of high- and low-spin population in solution. Specifically complex 4 is mostly high spin, while complexes 2 and 3 are of an intermediate spin state. The principal result of this paper is that with pressure the spin state of complex 4 changes from high spin (⁵T₂) to low spin (¹A₁). This change is monitored by following the changes with pressure in the metal-to-ligand charge-transfer bands of the complex which are at higher energy and lower intensity for a high-spin as compared to a low-spin complex. The effect of pressure on the metal-to-ligand charge-transfer (CT) bands of complexes 2, 3, and 4 has been studied in acetone and dichloromethane solutions. The pressure range studied is from 0.001 kbar to 10.0 kbar (1.0 kbar = 986.92 atm = 0.1 GPa). The predominant effect of pressure, in both media for all three complexes, is a shift to lower energy and an increase in intensity of the CT bands. The difference in magnitude for these spectral changes with pressure indicate that the predominantly high-spin complex 4 is converted to a low-spin complex in solution upon the application of pressure.

Original language	English (US)
Pages (from-to)	1738-1741
Number of pages	4
Journal	Journal of the American Chemical Society
Volume	111
Issue number	5
DOIs	https://doi.org/10.1021/ja00187a027
State	Published - Mar 1989

ASJC Scopus subject areas

Catalysis
General Chemistry
Biochemistry
Colloid and Surface Chemistry

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10.1021/ja00187a027

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@article{2663d8a504e8475e98edd9a6de21aaf6,

title = "Pressure-Induced Spin-State Interconversion of [Fe(6-Me-py)3tren](ClO4)2 in Solution",

abstract = "The series of pseudooctahedral FeII spin-crossover complexes [Fe(6-Me-py)3tren](ClO4)2(4), [Fe(6-Me- py)2Pytren](ClO4)2(3), and [Fe(6-Me-py)py2tren](ClO4)2(2) exhibit varying degrees of high- and low-spin population in solution. Specifically complex 4 is mostly high spin, while complexes 2 and 3 are of an intermediate spin state. The principal result of this paper is that with pressure the spin state of complex 4 changes from high spin (5T2) to low spin (1A1). This change is monitored by following the changes with pressure in the metal-to-ligand charge-transfer bands of the complex which are at higher energy and lower intensity for a high-spin as compared to a low-spin complex. The effect of pressure on the metal-to-ligand charge-transfer (CT) bands of complexes 2, 3, and 4 has been studied in acetone and dichloromethane solutions. The pressure range studied is from 0.001 kbar to 10.0 kbar (1.0 kbar = 986.92 atm = 0.1 GPa). The predominant effect of pressure, in both media for all three complexes, is a shift to lower energy and an increase in intensity of the CT bands. The difference in magnitude for these spectral changes with pressure indicate that the predominantly high-spin complex 4 is converted to a low-spin complex in solution upon the application of pressure.",

author = "Hammack, {William S.} and Conti, {Andrew J.} and Hendrickson, {David N.} and Drickamer, {Harry G.}",

year = "1989",

month = mar,

doi = "10.1021/ja00187a027",

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volume = "111",

pages = "1738--1741",

journal = "Journal of the American Chemical Society",

issn = "0002-7863",

publisher = "American Chemical Society",

number = "5",

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T1 - Pressure-Induced Spin-State Interconversion of [Fe(6-Me-py)3tren](ClO4)2 in Solution

AU - Hammack, William S.

AU - Conti, Andrew J.

AU - Hendrickson, David N.

AU - Drickamer, Harry G.

PY - 1989/3

Y1 - 1989/3

N2 - The series of pseudooctahedral FeII spin-crossover complexes [Fe(6-Me-py)3tren](ClO4)2(4), [Fe(6-Me- py)2Pytren](ClO4)2(3), and [Fe(6-Me-py)py2tren](ClO4)2(2) exhibit varying degrees of high- and low-spin population in solution. Specifically complex 4 is mostly high spin, while complexes 2 and 3 are of an intermediate spin state. The principal result of this paper is that with pressure the spin state of complex 4 changes from high spin (5T2) to low spin (1A1). This change is monitored by following the changes with pressure in the metal-to-ligand charge-transfer bands of the complex which are at higher energy and lower intensity for a high-spin as compared to a low-spin complex. The effect of pressure on the metal-to-ligand charge-transfer (CT) bands of complexes 2, 3, and 4 has been studied in acetone and dichloromethane solutions. The pressure range studied is from 0.001 kbar to 10.0 kbar (1.0 kbar = 986.92 atm = 0.1 GPa). The predominant effect of pressure, in both media for all three complexes, is a shift to lower energy and an increase in intensity of the CT bands. The difference in magnitude for these spectral changes with pressure indicate that the predominantly high-spin complex 4 is converted to a low-spin complex in solution upon the application of pressure.

AB - The series of pseudooctahedral FeII spin-crossover complexes [Fe(6-Me-py)3tren](ClO4)2(4), [Fe(6-Me- py)2Pytren](ClO4)2(3), and [Fe(6-Me-py)py2tren](ClO4)2(2) exhibit varying degrees of high- and low-spin population in solution. Specifically complex 4 is mostly high spin, while complexes 2 and 3 are of an intermediate spin state. The principal result of this paper is that with pressure the spin state of complex 4 changes from high spin (5T2) to low spin (1A1). This change is monitored by following the changes with pressure in the metal-to-ligand charge-transfer bands of the complex which are at higher energy and lower intensity for a high-spin as compared to a low-spin complex. The effect of pressure on the metal-to-ligand charge-transfer (CT) bands of complexes 2, 3, and 4 has been studied in acetone and dichloromethane solutions. The pressure range studied is from 0.001 kbar to 10.0 kbar (1.0 kbar = 986.92 atm = 0.1 GPa). The predominant effect of pressure, in both media for all three complexes, is a shift to lower energy and an increase in intensity of the CT bands. The difference in magnitude for these spectral changes with pressure indicate that the predominantly high-spin complex 4 is converted to a low-spin complex in solution upon the application of pressure.

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