Peripheral substitution: an easy way to tuning the magnetic behavior of tetrakis(phthalocyaninato) dysprosium(III) SMMs.

Hailong Wang,Suyuan Zeng,Jianmin Dou,Jianzhuang Jiang,Hong Shang

doi:10.1038/srep08838

Hailong Wang, Suyuan Zeng + Show 3 more

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https://doi.org/10.1038/srep08838

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Abstract

Two tetrakis(phthalocyaninato) dysprosium(III)-cadmium(II) single-molecule magnets (SMMs) with different extent of phthalocyanine peripheral substitution and therefore different coordination geometry for the Dy ions were revealed to exhibit different SMM behavior, providing an easy way to tuning and controlling the molecular structure and in turn the magnetic properties of tetrakis(tetrapyrrole) lanthanide SMMs through simple tetrapyrrole peripheral substitution.

Highlights

Two tetrakis(phthalocyaninato) dysprosium(III)-cadmium(II) single-molecule magnets (SMMs) with different extent of phthalocyanine peripheral substitution and different coordination geometry for the Dy ions were revealed to exhibit different SMM behavior, providing an easy way to tuning and controlling the molecular structure and in turn the magnetic properties of tetrakis(tetrapyrrole) lanthanide SMMs through simple tetrapyrrole peripheral substitution
A little later, a series of {(Pc)M1(Pc)Cd[phthalocyanine analogues (Pc)(OC4H9)8]M2[Pc(OC4H9)8]} (M1Cd-M2 5 Tb-Cd-Tb, Tb-Cd-Y, Y-Cd-Tb) SMMs were designed and synthesized for the purpose of clarifying the effect of long range f-f interaction between the two lanthanide ions separated by a diamagnetic ion on the magnetic properties[20]
Single crystal X-ray diffraction analysis clearly reveals the different skew angle for the bis(phthalocyaninato) dysprosium unit in these two quadrupledecker compounds. This in turn results in their obvious different SMM behavior according to magnetic meawww.nature.com/scientificreports surements, revealing the structure-magnetic property relationship but more importantly providing an easy but effective way towards effectively tuning the SMM behavior of tetrakis(phthalocyaninato) lanthanide quadruple-deckers through simple peripheral substitution

Summary

Introduction

Two tetrakis(phthalocyaninato) dysprosium(III)-cadmium(II) single-molecule magnets (SMMs) with different extent of phthalocyanine peripheral substitution and different coordination geometry for the Dy ions were revealed to exhibit different SMM behavior, providing an easy way to tuning and controlling the molecular structure and in turn the magnetic properties of tetrakis(tetrapyrrole) lanthanide SMMs through simple tetrapyrrole peripheral substitution. Results and Discussion In the present paper, with the aim of tuning and controlling the molecular structure ( the coordination geometry of the dysprosium spin carrier), two new tetrakis(phthalocyaninato) metal quadruple-decker complexes {(Pc)Dy[Pc(OC5H11)8]Cd[Pc(OC5H11)8]Dy(Pc)} (1) and {[Pc(OC5H11)8]Dy[Pc(OC5H11)8]Cd[Pc(OC5H11)8] Dy[Pc(OC5H11)8]} (2) {H2Pc 5 unsubstituted phthalocyanine; H2Pc(OC5H11)8 5 2,3,9,10,16,17,23,24-octakis (pentyloxy)phthalocyanine} with different extent of peripheral substitution for the phthalocyanine ligands have been designed and prepared from corresponding neutral bis(phthalocyaninato) dysprosium double-decker {(Pc)Dy[Pc(OC5H11)8]} or {[Pc(OC5H11)8]Dy[Pc(OC5H11)8]}, respectively, Figure 1.

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Conclusion