Magnetic properties of dendritic polycarbenes substituted by bulky peripheral groups

As photo-reactive precursors of high-spin organic compounds sterically separated from surroundings by bulky peripheral groups, diphenyldiazomethane derivatives substituted by tetrakis{3,5-bis(benzyloxy)benzyloxy} groups 1, by tetrakis[3,5-bis{3′,5′-bis(benzyloxy)benzyloxy}bezyloxy] groups 2, and nonakisdiazo compound associated with ferromagnetic spin couplers substituted by dodecakis{3,5-bis(benzyloxy)benzyloxy} groups 3, were prepared and their magnetic properties after irradiation in their own condensed films were investigated. Field dependences of magnetization and temperature dependences of χT value after irradiation of 1 and 2 clearly exhibited that spin centers i.e., diphenylcarbene parts of 1 and 2 were magnetically isolated from surrounding molecules each other by steric hindrance of the peripheral bulk substituents even in the neat films. In the case of 3, some part of molecules interacted antiferromagnetically with neighboring molecules but a fatal strong antiferromagnetic interaction was also avoided.

Graphical abstractThree photo-reactive precursors of high-spin organic compounds sterically separated from surroundings by Fréchet-type dendrons, bis{3,5-bis[3′,5′-bis(benzyloxy)benzyloxy]phenyl}diazomethane 1, bis{3,5-bis{3′,5′-bis[3″,5″-bis(benzyloxy)benzyloxy]bezyloxy}phenyl}diazomethane 2, and dodecakis[3,5-bis(benzyloxy)benzyloxy]nonakisdiazo compound 3, were prepared and their magnetic properties after irradiation in their own condensed films were investigated.Figure optionsDownload full-size imageDownload as PowerPoint slide