Auxiliary ligand-induced structural diversities of octacyanometalate-based heterobimetallic coordination polymers towards diverse magnetic properties

Jun Qian; Hirofumi Yoshikawa; Jingchun Hu; Mark G. Humphrey; Jinfang Zhang; Kunio Awaga; Chi Zhang

doi:10.1039/c9dt00654k

Auxiliary ligand-induced structural diversities of octacyanometalate-based heterobimetallic coordination polymers towards diverse magnetic properties

Jun Qian, Hirofumi Yoshikawa, Jingchun Hu, Mark G. Humphrey, Jinfang Zhang, Kunio Awaga, Chi Zhang^*

^*Corresponding author for this work

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

6 Citations (Scopus)

Abstract

Three octacyanometalate-based bimetallic coordination polymers (CPs), {[μ₄-M^V(CN)₈][Co(DMF)₄]₂(ClO₄)}_n (M = W CP-1, Mo CP-2) and {[μ₄-W^IV(CN)₈]Co₂(azpy)₄}_n CP-3, were synthesized in the absence (for CPs 1 and 2) or presence (for CP-3) of auxiliary ligand 4,4′-azopyridine (azpy), respectively. CPs 1 and 2 exhibit the same three-dimensional (3D) polymeric cation frameworks with [ClO₄]^- as the counterions, while CP-3 displays a porous 3D framework in an unusual 2-nodal (4,6)-connected 4,6T155 topology with point symbol as {4²·6⁴}{4⁶·6⁴·7·8⁴}₂. Notably is that octacyanometalate [W^V(CN)₈]^3- has been reduced into [W^IV(CN)₈]^4- during the synthetic process of CP-3. The magnetic investigations indicate that CP-1 exhibits the typical ferromagnetic property due to the ferromagnetic coupling between W(v) and Co(ii) spin centers, while CP-3 displays the weak ferromagnetic interaction at low temperature, which is consistent with the valence change of W center in CP-3.

Original language	English
Pages (from-to)	7666-7676
Number of pages	11
Journal	Dalton Transactions
Volume	48
Issue number	22
DOIs	https://doi.org/10.1039/c9dt00654k
Publication status	Published - 2019

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@article{120723a1ef3a41488beabca66ca8f1c1,

title = "Auxiliary ligand-induced structural diversities of octacyanometalate-based heterobimetallic coordination polymers towards diverse magnetic properties",

abstract = "Three octacyanometalate-based bimetallic coordination polymers (CPs), {[μ4-MV(CN)8][Co(DMF)4]2(ClO4)}n (M = W CP-1, Mo CP-2) and {[μ4-WIV(CN)8]Co2(azpy)4}n CP-3, were synthesized in the absence (for CPs 1 and 2) or presence (for CP-3) of auxiliary ligand 4,4′-azopyridine (azpy), respectively. CPs 1 and 2 exhibit the same three-dimensional (3D) polymeric cation frameworks with [ClO4]- as the counterions, while CP-3 displays a porous 3D framework in an unusual 2-nodal (4,6)-connected 4,6T155 topology with point symbol as {42·64}{46·64·7·84}2. Notably is that octacyanometalate [WV(CN)8]3- has been reduced into [WIV(CN)8]4- during the synthetic process of CP-3. The magnetic investigations indicate that CP-1 exhibits the typical ferromagnetic property due to the ferromagnetic coupling between W(v) and Co(ii) spin centers, while CP-3 displays the weak ferromagnetic interaction at low temperature, which is consistent with the valence change of W center in CP-3.",

author = "Jun Qian and Hirofumi Yoshikawa and Jingchun Hu and Humphrey, {Mark G.} and Jinfang Zhang and Kunio Awaga and Chi Zhang",

note = "Publisher Copyright: {\textcopyright} The Royal Society of Chemistry 2019.",

year = "2019",

doi = "10.1039/c9dt00654k",

language = "English",

volume = "48",

pages = "7666--7676",

journal = "Dalton Transactions",

issn = "1477-9226",

publisher = "Royal Society of Chemistry",

number = "22",

}

TY - JOUR

T1 - Auxiliary ligand-induced structural diversities of octacyanometalate-based heterobimetallic coordination polymers towards diverse magnetic properties

AU - Qian, Jun

AU - Yoshikawa, Hirofumi

AU - Hu, Jingchun

AU - Humphrey, Mark G.

AU - Zhang, Jinfang

AU - Awaga, Kunio

AU - Zhang, Chi

PY - 2019

Y1 - 2019

N2 - Three octacyanometalate-based bimetallic coordination polymers (CPs), {[μ4-MV(CN)8][Co(DMF)4]2(ClO4)}n (M = W CP-1, Mo CP-2) and {[μ4-WIV(CN)8]Co2(azpy)4}n CP-3, were synthesized in the absence (for CPs 1 and 2) or presence (for CP-3) of auxiliary ligand 4,4′-azopyridine (azpy), respectively. CPs 1 and 2 exhibit the same three-dimensional (3D) polymeric cation frameworks with [ClO4]- as the counterions, while CP-3 displays a porous 3D framework in an unusual 2-nodal (4,6)-connected 4,6T155 topology with point symbol as {42·64}{46·64·7·84}2. Notably is that octacyanometalate [WV(CN)8]3- has been reduced into [WIV(CN)8]4- during the synthetic process of CP-3. The magnetic investigations indicate that CP-1 exhibits the typical ferromagnetic property due to the ferromagnetic coupling between W(v) and Co(ii) spin centers, while CP-3 displays the weak ferromagnetic interaction at low temperature, which is consistent with the valence change of W center in CP-3.

AB - Three octacyanometalate-based bimetallic coordination polymers (CPs), {[μ4-MV(CN)8][Co(DMF)4]2(ClO4)}n (M = W CP-1, Mo CP-2) and {[μ4-WIV(CN)8]Co2(azpy)4}n CP-3, were synthesized in the absence (for CPs 1 and 2) or presence (for CP-3) of auxiliary ligand 4,4′-azopyridine (azpy), respectively. CPs 1 and 2 exhibit the same three-dimensional (3D) polymeric cation frameworks with [ClO4]- as the counterions, while CP-3 displays a porous 3D framework in an unusual 2-nodal (4,6)-connected 4,6T155 topology with point symbol as {42·64}{46·64·7·84}2. Notably is that octacyanometalate [WV(CN)8]3- has been reduced into [WIV(CN)8]4- during the synthetic process of CP-3. The magnetic investigations indicate that CP-1 exhibits the typical ferromagnetic property due to the ferromagnetic coupling between W(v) and Co(ii) spin centers, while CP-3 displays the weak ferromagnetic interaction at low temperature, which is consistent with the valence change of W center in CP-3.

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U2 - 10.1039/c9dt00654k

DO - 10.1039/c9dt00654k

M3 - Article

SN - 1477-9226

VL - 48

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EP - 7676

JO - Dalton Transactions

JF - Dalton Transactions

IS - 22

ER -

Auxiliary ligand-induced structural diversities of octacyanometalate-based heterobimetallic coordination polymers towards diverse magnetic properties

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