Structural and kinetic study of reversible CO2 fixation by dicopper macrocyclic complexes. From intramolecular binding to self-assembly of molecular boxes

Anna Company; Joo Eun Jee; Xavi Ribas; Josep Maria Lopez-Valbuena; Laura Gómez; Montserrat Corbella; Antoni Llobet; José Mahía; Jordi Benet-Buchholz; Miquel Costas; Rudi Van Eldik

doi:10.1021/ic700692t

Structural and kinetic study of reversible CO₂ fixation by dicopper macrocyclic complexes. From intramolecular binding to self-assembly of molecular boxes

Anna Company
, Joo Eun Jee
, Xavi Ribas
, Josep Maria Lopez-Valbuena
, Laura Gómez
, Montserrat Corbella
, Antoni Llobet
, José Mahía
, Jordi Benet-Buchholz
, Miquel Costas
, Rudi Van Eldik

Department of Chemistry

Friedrich-Alexander University Erlangen-Nürnberg
University of Girona
Campus Universitari
University of Barcelona
Autonomous University of Barcelona
University of A Coruna

Research output: Contribution to journal › Scientific article › peer-review

51 Citations (Scopus)

Abstract

A study of the reversible CO₂ fixation by a series of macrocyclic dicopper complexes is described. The dicopper macrocyclic complexes [Cu₂(OH)₂(Me2p)](CF₃SO₃) ₂, 1(CF₃SO₃)₂, and [Cu ₂(μ-OH)₂(Me2m)](CF₃SO₃) ₂, 2(CF₃SO₃)₂, (Scheme 1) containing terminally bound and bridging hydroxide ligands, respectively, promote reversible inter- and intramolecular CO₂ fixation that results in the formation of the carbonate complexes [{Cu₂(Me2p)} ₂(μ-CO₃)₂](CF₃SO ₃)₄, 4(CF₃SO₃)₄, and [Cu₂(μ-CO₃)(Me2m)](CF₃SO₃) ₂, 5(CF₃SO₃)₂. Under a N₂ atmosphere the complexes evolve CO₂ and revert to the starting hydroxo complexes 1(CF₃SO₃)₂ and 2(CF ₃SO₃)₂, a reaction the rate of which linearly depends on [H₂O]. In the presence of water, attempts to crystallize 5(CF₃SO₃)₂ afford [{Cu₂(Me2m)(H ₂O)}₂(μ-CO₃)₂](CF ₃SO₃)₄, 6(CF₃SO₃) ₄, which appears to rapidly convert to 5(CF₃SO ₃)₂ in acetonitrile solution. [Cu₂(OH) ₂(H3m)]²⁺, 7, which contains a larger macrocyclic ligand, irreversibly reacts with atmospheric CO₂ to generate cagelike [{Cu₂(H3m)}₂(μ-CO₃)₂](ClO ₄)₄, 8(ClO₄)₄. However, addition of 1 equiv of HClO₄ per Cu generates [Cu₂(H3m)(CH ₃CN)₄]⁴⁺ (3), and subsequent addition of Et₃N under air reassembles 8. The carbonate complexes 4(CF ₃SO₃)₄, 5(CF₃SO₃) ₂, 6(CF₃SO₃)₄, and 8(ClO ₄)₄ have been characterized in the solid state by X-ray crystallography. This analysis reveals that 4(CF₃SO₃) ₄, 6(CF₃SO₃)₄, and 8(ClO ₄)₄ consist of self-assembled molecular boxes containing two macrocyclic dicopper complexes, bridged by CO₃ ^2- ligands. The bridging mode of the carbonate ligand is anti-anti-μ- η¹:η¹ in 4(CF₃SO₃) ₄, anti-anti-μ-η²:η¹ in 6(CF ₃SO₃)₄ and anti-anti-μ-η²: η² in 5(CF₃SO₃)₂ and 8(ClO ₄)₄. Magnetic susceptibility measurements on 4(CF ₃SO₃)₄, 6(CF₃SO₃) ₄, and 8(ClO₄)₄ indicate that the carbonate ligands mediate antiferromagnetic coupling between each pair of bridged Cu ^II ions (J = -23.1, -108.3, and -163.4 cm^-1, respectively, H = -JS₁S₂). Detailed kinetic analyses of the reaction between carbon dioxide and the macrocyclic complexes 1(CF₃SO ₃)₂ and 2(CF₃SO₃)₂ suggest that it is actually hydrogen carbonate formed in aqueous solution on dissolving CO₂ that is responsible for the observed formation of the different carbonate complexes controlled by the binding mode of the hydroxy ligands. This study shows that CO₂ fixation can be used as an on/off switch for the reversible self-assembly of supramolecular structures based on macrocyclic dicopper complexes.

Original language	English
Pages (from-to)	9098-9110
Number of pages	13
Journal	Inorganic Chemistry
Volume	46
Issue number	22
DOIs	https://doi.org/10.1021/ic700692t
Publication status	Published - 29 Oct 2007

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10.1021/ic700692t

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Company, A., Jee, J. E., Ribas, X., Lopez-Valbuena, J. M., Gómez, L., Corbella, M., Llobet, A., Mahía, J., Benet-Buchholz, J., Costas, M., & Van Eldik, R. (2007). Structural and kinetic study of reversible CO₂ fixation by dicopper macrocyclic complexes. From intramolecular binding to self-assembly of molecular boxes. Inorganic Chemistry, 46(22), 9098-9110. https://doi.org/10.1021/ic700692t

@article{5fc26324f20143dfa83670e45be9312b,

title = "Structural and kinetic study of reversible CO2 fixation by dicopper macrocyclic complexes. From intramolecular binding to self-assembly of molecular boxes",

abstract = "A study of the reversible CO2 fixation by a series of macrocyclic dicopper complexes is described. The dicopper macrocyclic complexes [Cu2(OH)2(Me2p)](CF3SO3) 2, 1(CF3SO3)2, and [Cu 2(μ-OH)2(Me2m)](CF3SO3) 2, 2(CF3SO3)2, (Scheme 1) containing terminally bound and bridging hydroxide ligands, respectively, promote reversible inter- and intramolecular CO2 fixation that results in the formation of the carbonate complexes [\{Cu2(Me2p)\} 2(μ-CO3)2](CF3SO 3)4, 4(CF3SO3)4, and [Cu2(μ-CO3)(Me2m)](CF3SO3) 2, 5(CF3SO3)2. Under a N2 atmosphere the complexes evolve CO2 and revert to the starting hydroxo complexes 1(CF3SO3)2 and 2(CF 3SO3)2, a reaction the rate of which linearly depends on [H2O]. In the presence of water, attempts to crystallize 5(CF3SO3)2 afford [\{Cu2(Me2m)(H 2O)\}2(μ-CO3)2](CF 3SO3)4, 6(CF3SO3) 4, which appears to rapidly convert to 5(CF3SO 3)2 in acetonitrile solution. [Cu2(OH) 2(H3m)]2+, 7, which contains a larger macrocyclic ligand, irreversibly reacts with atmospheric CO2 to generate cagelike [\{Cu2(H3m)\}2(μ-CO3)2](ClO 4)4, 8(ClO4)4. However, addition of 1 equiv of HClO4 per Cu generates [Cu2(H3m)(CH 3CN)4]4+ (3), and subsequent addition of Et3N under air reassembles 8. The carbonate complexes 4(CF 3SO3)4, 5(CF3SO3) 2, 6(CF3SO3)4, and 8(ClO 4)4 have been characterized in the solid state by X-ray crystallography. This analysis reveals that 4(CF3SO3) 4, 6(CF3SO3)4, and 8(ClO 4)4 consist of self-assembled molecular boxes containing two macrocyclic dicopper complexes, bridged by CO3 2- ligands. The bridging mode of the carbonate ligand is anti-anti-μ- η1:η1 in 4(CF3SO3) 4, anti-anti-μ-η2:η1 in 6(CF 3SO3)4 and anti-anti-μ-η2: η2 in 5(CF3SO3)2 and 8(ClO 4)4. Magnetic susceptibility measurements on 4(CF 3SO3)4, 6(CF3SO3) 4, and 8(ClO4)4 indicate that the carbonate ligands mediate antiferromagnetic coupling between each pair of bridged Cu II ions (J = -23.1, -108.3, and -163.4 cm-1, respectively, H = -JS1S2). Detailed kinetic analyses of the reaction between carbon dioxide and the macrocyclic complexes 1(CF3SO 3)2 and 2(CF3SO3)2 suggest that it is actually hydrogen carbonate formed in aqueous solution on dissolving CO2 that is responsible for the observed formation of the different carbonate complexes controlled by the binding mode of the hydroxy ligands. This study shows that CO2 fixation can be used as an on/off switch for the reversible self-assembly of supramolecular structures based on macrocyclic dicopper complexes.",

author = "Anna Company and Jee, \{Joo Eun\} and Xavi Ribas and Lopez-Valbuena, \{Josep Maria\} and Laura G{\'o}mez and Montserrat Corbella and Antoni Llobet and Jos{\'e} Mah{\'i}a and Jordi Benet-Buchholz and Miquel Costas and \{Van Eldik\}, Rudi",

year = "2007",

month = oct,

day = "29",

doi = "10.1021/ic700692t",

language = "English",

volume = "46",

pages = "9098--9110",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "22",

}

Company, A, Jee, JE, Ribas, X, Lopez-Valbuena, JM, Gómez, L, Corbella, M, Llobet, A, Mahía, J, Benet-Buchholz, J, Costas, M & Van Eldik, R 2007, 'Structural and kinetic study of reversible CO₂ fixation by dicopper macrocyclic complexes. From intramolecular binding to self-assembly of molecular boxes', Inorganic Chemistry, vol. 46, no. 22, pp. 9098-9110. https://doi.org/10.1021/ic700692t

TY - JOUR

T1 - Structural and kinetic study of reversible CO2 fixation by dicopper macrocyclic complexes. From intramolecular binding to self-assembly of molecular boxes

AU - Company, Anna

AU - Jee, Joo Eun

AU - Ribas, Xavi

AU - Lopez-Valbuena, Josep Maria

AU - Gómez, Laura

AU - Corbella, Montserrat

AU - Llobet, Antoni

AU - Mahía, José

AU - Benet-Buchholz, Jordi

AU - Costas, Miquel

AU - Van Eldik, Rudi

PY - 2007/10/29

Y1 - 2007/10/29

N2 - A study of the reversible CO2 fixation by a series of macrocyclic dicopper complexes is described. The dicopper macrocyclic complexes [Cu2(OH)2(Me2p)](CF3SO3) 2, 1(CF3SO3)2, and [Cu 2(μ-OH)2(Me2m)](CF3SO3) 2, 2(CF3SO3)2, (Scheme 1) containing terminally bound and bridging hydroxide ligands, respectively, promote reversible inter- and intramolecular CO2 fixation that results in the formation of the carbonate complexes [{Cu2(Me2p)} 2(μ-CO3)2](CF3SO 3)4, 4(CF3SO3)4, and [Cu2(μ-CO3)(Me2m)](CF3SO3) 2, 5(CF3SO3)2. Under a N2 atmosphere the complexes evolve CO2 and revert to the starting hydroxo complexes 1(CF3SO3)2 and 2(CF 3SO3)2, a reaction the rate of which linearly depends on [H2O]. In the presence of water, attempts to crystallize 5(CF3SO3)2 afford [{Cu2(Me2m)(H 2O)}2(μ-CO3)2](CF 3SO3)4, 6(CF3SO3) 4, which appears to rapidly convert to 5(CF3SO 3)2 in acetonitrile solution. [Cu2(OH) 2(H3m)]2+, 7, which contains a larger macrocyclic ligand, irreversibly reacts with atmospheric CO2 to generate cagelike [{Cu2(H3m)}2(μ-CO3)2](ClO 4)4, 8(ClO4)4. However, addition of 1 equiv of HClO4 per Cu generates [Cu2(H3m)(CH 3CN)4]4+ (3), and subsequent addition of Et3N under air reassembles 8. The carbonate complexes 4(CF 3SO3)4, 5(CF3SO3) 2, 6(CF3SO3)4, and 8(ClO 4)4 have been characterized in the solid state by X-ray crystallography. This analysis reveals that 4(CF3SO3) 4, 6(CF3SO3)4, and 8(ClO 4)4 consist of self-assembled molecular boxes containing two macrocyclic dicopper complexes, bridged by CO3 2- ligands. The bridging mode of the carbonate ligand is anti-anti-μ- η1:η1 in 4(CF3SO3) 4, anti-anti-μ-η2:η1 in 6(CF 3SO3)4 and anti-anti-μ-η2: η2 in 5(CF3SO3)2 and 8(ClO 4)4. Magnetic susceptibility measurements on 4(CF 3SO3)4, 6(CF3SO3) 4, and 8(ClO4)4 indicate that the carbonate ligands mediate antiferromagnetic coupling between each pair of bridged Cu II ions (J = -23.1, -108.3, and -163.4 cm-1, respectively, H = -JS1S2). Detailed kinetic analyses of the reaction between carbon dioxide and the macrocyclic complexes 1(CF3SO 3)2 and 2(CF3SO3)2 suggest that it is actually hydrogen carbonate formed in aqueous solution on dissolving CO2 that is responsible for the observed formation of the different carbonate complexes controlled by the binding mode of the hydroxy ligands. This study shows that CO2 fixation can be used as an on/off switch for the reversible self-assembly of supramolecular structures based on macrocyclic dicopper complexes.

AB - A study of the reversible CO2 fixation by a series of macrocyclic dicopper complexes is described. The dicopper macrocyclic complexes [Cu2(OH)2(Me2p)](CF3SO3) 2, 1(CF3SO3)2, and [Cu 2(μ-OH)2(Me2m)](CF3SO3) 2, 2(CF3SO3)2, (Scheme 1) containing terminally bound and bridging hydroxide ligands, respectively, promote reversible inter- and intramolecular CO2 fixation that results in the formation of the carbonate complexes [{Cu2(Me2p)} 2(μ-CO3)2](CF3SO 3)4, 4(CF3SO3)4, and [Cu2(μ-CO3)(Me2m)](CF3SO3) 2, 5(CF3SO3)2. Under a N2 atmosphere the complexes evolve CO2 and revert to the starting hydroxo complexes 1(CF3SO3)2 and 2(CF 3SO3)2, a reaction the rate of which linearly depends on [H2O]. In the presence of water, attempts to crystallize 5(CF3SO3)2 afford [{Cu2(Me2m)(H 2O)}2(μ-CO3)2](CF 3SO3)4, 6(CF3SO3) 4, which appears to rapidly convert to 5(CF3SO 3)2 in acetonitrile solution. [Cu2(OH) 2(H3m)]2+, 7, which contains a larger macrocyclic ligand, irreversibly reacts with atmospheric CO2 to generate cagelike [{Cu2(H3m)}2(μ-CO3)2](ClO 4)4, 8(ClO4)4. However, addition of 1 equiv of HClO4 per Cu generates [Cu2(H3m)(CH 3CN)4]4+ (3), and subsequent addition of Et3N under air reassembles 8. The carbonate complexes 4(CF 3SO3)4, 5(CF3SO3) 2, 6(CF3SO3)4, and 8(ClO 4)4 have been characterized in the solid state by X-ray crystallography. This analysis reveals that 4(CF3SO3) 4, 6(CF3SO3)4, and 8(ClO 4)4 consist of self-assembled molecular boxes containing two macrocyclic dicopper complexes, bridged by CO3 2- ligands. The bridging mode of the carbonate ligand is anti-anti-μ- η1:η1 in 4(CF3SO3) 4, anti-anti-μ-η2:η1 in 6(CF 3SO3)4 and anti-anti-μ-η2: η2 in 5(CF3SO3)2 and 8(ClO 4)4. Magnetic susceptibility measurements on 4(CF 3SO3)4, 6(CF3SO3) 4, and 8(ClO4)4 indicate that the carbonate ligands mediate antiferromagnetic coupling between each pair of bridged Cu II ions (J = -23.1, -108.3, and -163.4 cm-1, respectively, H = -JS1S2). Detailed kinetic analyses of the reaction between carbon dioxide and the macrocyclic complexes 1(CF3SO 3)2 and 2(CF3SO3)2 suggest that it is actually hydrogen carbonate formed in aqueous solution on dissolving CO2 that is responsible for the observed formation of the different carbonate complexes controlled by the binding mode of the hydroxy ligands. This study shows that CO2 fixation can be used as an on/off switch for the reversible self-assembly of supramolecular structures based on macrocyclic dicopper complexes.

UR - https://www.scopus.com/pages/publications/35848950976

U2 - 10.1021/ic700692t

DO - 10.1021/ic700692t

M3 - Scientific article

C2 - 17914857

AN - SCOPUS:35848950976

SN - 0020-1669

VL - 46

SP - 9098

EP - 9110

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 22

ER -

Structural and kinetic study of reversible CO₂ fixation by dicopper macrocyclic complexes. From intramolecular binding to self-assembly of molecular boxes

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