Issue 34, 2018

Cross-linking of cyanide magnetic coordination polymers by rational insertion of formate, cyanide or azide

Abstract

Carefully selected molecular bridging ligands formate, cyanide and azide, that are known to transmit strong magnetic interactions, have been successfully inserted into the {[MnII(H2O)2]2[NbIV(CN)8]·4H2O}n (Mn2Nb) ferrimagnetic parent framework, resulting in the additional molecular bridging of the two MnII centres in three new coordination polymers: {(NH4)[(H2O)MnII-(μ-HCOO)-MnII(H2O)][NbIV(CN)8]·3H2O}nMn2NbHCOO, {(NH4)[(NH3)MnII-(μ-CN)-MnII(H2O)][NbIV(CN)8]·2H2O}nMn2NbCN and {(NH4)[(H2O)MnII-(μ-N3)-MnII(H2O)][NbIV(CN)8]·3H2O}nMn2NbN3. The extra bridging ligands cross-linking the two MnII centers strongly influence the long-range ferrimagnetic order of the NbIV–CN–MnII parent framework by introducing competing antiferromagnetic interactions. The values of the JMnMn constants were obtained by fitting the magnetic properties of the MoIV congeners {(NH4)[(H2O)MnII-(μ-HCOO)-MnII(H2O)][MoIV(CN)8]·3H2O}nMn2MoHCOO, {(NH4)[(NH3)MnII-(μ-CN)-MnII(H2O)][MoIV(CN)8]·2H2O}nMn2MoCN and {(NH4)[(H2O)MnII-(μ-N3)-MnII(H2O)][MoIV(CN)8]·3H2O}nMn2MoN3, where the paramagnetic NbIV was substituted by the diamagnetic MoIV, thus disabling the long-range magnetic ordering of the CN-framework. Our strategy demonstrates how chemists can control the magnetic behavior of molecular magnets by subtle and rational structural modification based on chemical knowledge.

Graphical abstract: Cross-linking of cyanide magnetic coordination polymers by rational insertion of formate, cyanide or azide

Supplementary files

Article information

Article type
Paper
Submitted
17 4 2018
Accepted
21 5 2018
First published
21 5 2018

Dalton Trans., 2018,47, 11888-11894

Cross-linking of cyanide magnetic coordination polymers by rational insertion of formate, cyanide or azide

G. Handzlik, B. Sieklucka and D. Pinkowicz, Dalton Trans., 2018, 47, 11888 DOI: 10.1039/C8DT01513A

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