Non-Linear optical (NLO) Active Ferrocene system

Active ferrocene engineering was based on understanding of physical forms such as

electrostatic interaction, hydrogen bonding and charge transfer. Vander Waals interaction and pi-
pi heap is a powerful technique for the production of functionalized solid materials with
optimized properties. It has been applied to various organometallic compounds. Weak pi bonding
between metals and ligands forms various organometallic structures and packing modes
depending up on the solid state of intra and inter-molecular non-bonding interactions. The
significance of an electron donating strength of the organometallic compounds. It is consider as a
good donor part of a donor –Π acceptor system for chromophore with high Non-Linear optical
responses [168-169]. Ferrocene adopt various conformations, depending on the magnitude of the
rotational barrier and are regarded in a sense as non-rigid molecules that have variable structure.

: Ferrocene based ligands in Catalysis

The last ten years there have been a growing interest in amino phosphine compounds for
their asymmetric synthesis. Using precatalyst [Ru(C 6H6)Cl2] and the ferrocenyl based
aminophosphines ligand[170], they found that the hydrogenation proceeded efficiently with
reasonable enantioselectivity. An attractive feature of all such ferrocenyl aminophosphines is
their remarkable stability towards air oxidation, as samples containing these compounds exposed
to air up to three years shows no less enantioselectivity or activity in rhodium catalyzed
hydrogenation[171].

: Ferrocene and Its Redox Properties

Ferrocene, also known as dicyclopentadienyl iron, has the primary chemical formula
C10H10Fe with a characteristic orange colour at room temperature. Ferrocene, a crystalline
diamagnetic solid is considered as the most stable of all the metallocenes with 18 valence electrons
and has a boiling point of 249 oC, a melting point of 173-174 oC. It sublimes readily and is stable to
air or water, which makes purifying the products quite an easy task but can be, oxidized reversibly.
The most important property of ferrocene is its redox property which has popularized this
compound. The electron transfer-reactive oxygen species-oxidative stress theory (ET-ROS-OS)
has been implicated in the mechanism of action of a wide variety of biologically active
compounds, for example nitroaromatics and quinones. Therefore, the development of drugs that
enhance Reactive Oxygen Species (ROS) has increased in importance. Also the fact that cancer
tissue is known to be in a state of oxidative stress further increases the need for new drugs that can
exploit this fact[30]. Increasing the concentration of ROS may overwhelm the cancer cells but
leave normal cells unaffected. Elevated levels of ROS are also known to induce apoptosis. Current
attention is given on increasing concentration of ROS to lethal levels in cells, interfering with anti-
oxidant enzymes and the promotion of catalysts that enhance the toxicity of the ROS. The loss of
an electron from a high energy, non-bonding orbital to yield the ferricenium cation, (Fe Fe), is
an important aspect of the chemistry of ferrocene and is often implicated in its cytotoxicity [172].

In biological systems ferrocene can be oxidized by hydrogen peroxide in the presence of

horseradish peroxidase, found in the roots of horseradish, have been extensively studied. The
hydroxyl radicals formed from Fe2+ under physiological conditions are proposed to act as DNA
damaging agents for biologically active ferrocene derivatives. The ferrocenium cation have been
shown to form charge transfer complexes with donor groups in proteins. The reverse reaction,
(Fc+ Fc), is known to proceed through oxidation of metalloproteins, in the presence of
glutathione forming hydroxyl radicals and through oxidation of NADH to NAD+. The oxidation
 of NADH to NAD+ is a good indicator of the ferrocenium cations capacity for interfering with
biologically important, enzyme controlled electron transfer reactions.

The redox status of a given biological system is vitally important as numerous processes in living
cells are mediated by redox reactions. For example, cellular respiration whereby ATP is formed
involves a series of reactions including the reduction of NAD+ and oxygen and the oxidation of
sugars. Redox activation of otherwise inactive prodrugs coupled with further chemical modification
e.g. hydrolysis, can lead to highly reactive electrophilic compounds. Suitable bio-redox prodrugs
should have minimal toxicity to healthy cells, stability to metabolism in aerobic cells and suitable
bioavailability and pharmacological properties.