Modulation of redox potentials utilizing the flexible coordination sphere of a penta-coordinate complex in the solid state

Ryo Ohtani; Yuu Kitamura; Yuh Hijikata; Masaaki Nakamura; Leonard F. Lindoy; Shinya Hayami

doi:10.1039/c7dt00233e

Modulation of redox potentials utilizing the flexible coordination sphere of a penta-coordinate complex in the solid state

Ryo Ohtani, Yuu Kitamura, Yuh Hijikata, Masaaki Nakamura, Leonard F. Lindoy, Shinya Hayami

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

4 Citations (Scopus)

Abstract

Slight changes in the coordination structure of the manganese(v)-nitrido anionic complex, [Mn^V(N)(CN)₄]²⁻, induced by using a “lipid package” approach markedly made an impact on the corresponding redox potentials. The single crystals of four lipid assemblies, [dabco-(CH₂)_n−1-CH₃]₂[Mn(N)(CN)₄(H₂O)]·xH₂O (n = 15, 16, 17 and 18; dabco = 1,4-diazabicyclo[2,2,2]octane), were synthesized and solid-state cyclic voltammetric studies demonstrated that the [Mn^V(N)(CN)₄]²⁻ anions with smaller “cross” NC-Mn-CN bond angles exhibit higher redox potentials. The observed trend reflects the energy change associated with the structural transformation from [Mn^V(N)(CN)₄]²⁻ to [Mn^VI(N)(CN)₄]²⁻ and is supported by the results of DFT calculations. The NC-Mn-CN bond angles in the flexible [Mn(N)(CN)₄]²⁻ structure exhibit excellent correlation with the redox potentials of the complexes in the solid state.

Original language	English
Pages (from-to)	3749-3754
Number of pages	6
Journal	Dalton Transactions
Volume	46
Issue number	11
DOIs	https://doi.org/10.1039/c7dt00233e
Publication status	Published - 2017
Externally published	Yes

All Science Journal Classification (ASJC) codes

Inorganic Chemistry

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10.1039/c7dt00233e

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@article{0a654a9955114c93920130b25e2cd387,

title = "Modulation of redox potentials utilizing the flexible coordination sphere of a penta-coordinate complex in the solid state",

abstract = "Slight changes in the coordination structure of the manganese(v)-nitrido anionic complex, [MnV(N)(CN)4]2−, induced by using a “lipid package” approach markedly made an impact on the corresponding redox potentials. The single crystals of four lipid assemblies, [dabco-(CH2)n−1-CH3]2[Mn(N)(CN)4(H2O)]·xH2O (n = 15, 16, 17 and 18; dabco = 1,4-diazabicyclo[2,2,2]octane), were synthesized and solid-state cyclic voltammetric studies demonstrated that the [MnV(N)(CN)4]2− anions with smaller “cross” NC-Mn-CN bond angles exhibit higher redox potentials. The observed trend reflects the energy change associated with the structural transformation from [MnV(N)(CN)4]2− to [MnVI(N)(CN)4]2− and is supported by the results of DFT calculations. The NC-Mn-CN bond angles in the flexible [Mn(N)(CN)4]2− structure exhibit excellent correlation with the redox potentials of the complexes in the solid state.",

author = "Ryo Ohtani and Yuu Kitamura and Yuh Hijikata and Masaaki Nakamura and Lindoy, {Leonard F.} and Shinya Hayami",

note = "Funding Information: This work was supported by JSPS Grant-in-Aid for Young Scientists (B) JP15K17833 and JSPS Grant-in-Aid for Scientific Research on Innovative Areas (Dynamical Ordering & Integrated Functions) JP16H00777. This work was also supported by KAKENHI Grant-in-Aid for Scientific Research (B) JP26288026. This work was partially supported by the Cooperative Research Program of {\textquoteleft}Network Joint Research Centre for Materials and Devices{\textquoteright}. Publisher Copyright: {\textcopyright} The Royal Society of Chemistry.",

year = "2017",

doi = "10.1039/c7dt00233e",

language = "English",

volume = "46",

pages = "3749--3754",

journal = "Dalton Transactions",

issn = "1477-9226",

publisher = "Royal Society of Chemistry",

number = "11",

}

TY - JOUR

T1 - Modulation of redox potentials utilizing the flexible coordination sphere of a penta-coordinate complex in the solid state

AU - Ohtani, Ryo

AU - Kitamura, Yuu

AU - Hijikata, Yuh

AU - Nakamura, Masaaki

AU - Lindoy, Leonard F.

AU - Hayami, Shinya

N1 - Funding Information: This work was supported by JSPS Grant-in-Aid for Young Scientists (B) JP15K17833 and JSPS Grant-in-Aid for Scientific Research on Innovative Areas (Dynamical Ordering & Integrated Functions) JP16H00777. This work was also supported by KAKENHI Grant-in-Aid for Scientific Research (B) JP26288026. This work was partially supported by the Cooperative Research Program of ‘Network Joint Research Centre for Materials and Devices’. Publisher Copyright: © The Royal Society of Chemistry.

PY - 2017

Y1 - 2017

N2 - Slight changes in the coordination structure of the manganese(v)-nitrido anionic complex, [MnV(N)(CN)4]2−, induced by using a “lipid package” approach markedly made an impact on the corresponding redox potentials. The single crystals of four lipid assemblies, [dabco-(CH2)n−1-CH3]2[Mn(N)(CN)4(H2O)]·xH2O (n = 15, 16, 17 and 18; dabco = 1,4-diazabicyclo[2,2,2]octane), were synthesized and solid-state cyclic voltammetric studies demonstrated that the [MnV(N)(CN)4]2− anions with smaller “cross” NC-Mn-CN bond angles exhibit higher redox potentials. The observed trend reflects the energy change associated with the structural transformation from [MnV(N)(CN)4]2− to [MnVI(N)(CN)4]2− and is supported by the results of DFT calculations. The NC-Mn-CN bond angles in the flexible [Mn(N)(CN)4]2− structure exhibit excellent correlation with the redox potentials of the complexes in the solid state.

AB - Slight changes in the coordination structure of the manganese(v)-nitrido anionic complex, [MnV(N)(CN)4]2−, induced by using a “lipid package” approach markedly made an impact on the corresponding redox potentials. The single crystals of four lipid assemblies, [dabco-(CH2)n−1-CH3]2[Mn(N)(CN)4(H2O)]·xH2O (n = 15, 16, 17 and 18; dabco = 1,4-diazabicyclo[2,2,2]octane), were synthesized and solid-state cyclic voltammetric studies demonstrated that the [MnV(N)(CN)4]2− anions with smaller “cross” NC-Mn-CN bond angles exhibit higher redox potentials. The observed trend reflects the energy change associated with the structural transformation from [MnV(N)(CN)4]2− to [MnVI(N)(CN)4]2− and is supported by the results of DFT calculations. The NC-Mn-CN bond angles in the flexible [Mn(N)(CN)4]2− structure exhibit excellent correlation with the redox potentials of the complexes in the solid state.

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U2 - 10.1039/c7dt00233e

DO - 10.1039/c7dt00233e

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C2 - 28262891

AN - SCOPUS:85015710527

SN - 1477-9226

VL - 46

SP - 3749

EP - 3754

JO - Dalton Transactions

JF - Dalton Transactions

IS - 11

ER -

Modulation of redox potentials utilizing the flexible coordination sphere of a penta-coordinate complex in the solid state

Abstract

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