Toward an iron(II) spin-crossover grafted phosphazene polymer.
Two new cyclotriphosphazene ligands with pendant 2,2':6',2″-terpyridine (Terpy) moieties, namely, (pentaphenoxy){4-[2,6-bis(2-pyridyl)]pyridoxy}cyclotriphosphazene (L(1)), (pentaphenoxy){4-[2,6-terpyridin-4-yl]phenoxy}cyclotriphosphazene (L(2)), and their respective polymeric analogues, L(1P) and L(2P), were synthesized. These ligands were used to form iron(II) complexes with an Fe(II)Terpy(2) core. Variable-temperature resonance Raman, UV-visible, and Mössbauer spectroscopies with magnetic measurements aided by density functional theory calculations were used to understand the physical characteristics of the complexes. By a comparison of measurements, the polymers were shown to behave in the same way as the cyclotriphosphazene analogues. The results showed that spin crossover (SCO) can be induced to start at high temperatures by extending the spacer length of the ligand to that in L(2) and L(2P); this combination provides a route to forming a malleable SCO material.
Chemistry-Institute of Fundamental Sciences, Massey University, Private Bag 11 222, Palmerston North 4442, New Zealand.
Ross J
RJ
Davidson
Eric W
EW
Ainscough
Andrew M
AM
Brodie
Geoffrey B
GB
Jameson
Mark R
MR
Waterland
Harry R
HR
Allcock
Mark D
MD
Hindenlang
Boujemaa
B
Moubaraki
Keith S
KS
Murray
Keith C
KC
Gordon
Raphael
R
Horvath
Guy N L
GN
Jameson