Synthesis and Crystal Engineering of Spin Switchable Fe(III) Complexes

The ligand is synthesised in situ from the Schiff base condensation of salicylaldehyde and 2-
hydrazinopyridine in methanol.

We will be synthesising octahedral Fe(III) complexes with an N 4O22- coordination sphere. The Fe(III)
oxidation is balance by two phenolates and a spectator anion.

We will be changing the anion to look at the effect it has on the packing and therefore spin state
change in the complexes.

We will be looking at a spin state change from high spin S = 5/2 at high temperature to low spin S =
½ at low temperatures and what type of transition behaviour is: gradual; abrupt; hysteretic; two-
step; incomplete.

Your project will focus on a set of different aldehydes and then synthesising the different anion salts
of the given complex.

Cl and NO3 salt will use the ferric chloride and ferric nitrate, respectively. For all other salts a
metathesis with an appropriate salt will be done during the reaction

General complex synthesis for Cl salt

X-salicylaldehyde (1 mmol) was added to 20 ml of methanol containing 2-hydrazinopyridine (1

mmol). This was stirred for 5 mins then 0.5 mmol of ferric chloride hexahydrate was added resulting
in a dark colour forming. This was stirred for a further 10 min then gravity filter through a fluted
filter paper and left to slowly evaporating to give crystals.

General complex synthesis for other (not Cl or NO3) anion salt

X-salicylaldehyde (1 mmol) was added to 20 ml of methanol containing 2-hydrazinopyridine (1

mmol). This was stirred for 5 mins then 0.5 mmol of ferric chloride hexahydrate was added resulting
in a dark colour forming. Immediately, 1 mmol of the appropriate sodium or ammonium salt was
added to the solution. This was stirred for a further 10 min then gravity filter through a fluted filter
paper and left to slowly evaporating to give crystals.
Your work will be on:

Salicylaldehyde

3-Methoxysalicyaldehyde

4-Methoxysalicyaldehyde

5-Methoxysalicyaldehyde

This will look at the effect of the steric and electronic effect on an electron donating group on spin
state