Kinetical and mechanical

aspects of metal helicates

Ana-Marija Bartolincic(Mia
Vikki,AMBLab)

Content

Introduction
Specifity of metal helicates
Mechanical aspects of metal helicates
Kinetical aspects of metal helicates
Characterisation of metal helicates using
analytical methods
Usage
Conclusion
References

Introduction

Term called halicate have been deployed

for the first time by Lehn et al.in 1987 to
describe double stranded polymetal helix
and defining a metal contained helix
The word helix comes from greece word
meaning helicoidal, turned, strand,coil,
and added ate at the end to actually
define :guest host complexes between
organisied receptors and metal ions

Introduction

The term helicates also include specific

bonding in types of compounds like:
Coronates (macrocylic compounds or
macrocyclic compounds of Na/K group)
Cryptates (macropolycyclic complexes
with one or more inclusional metal
ions)

Introduction

Picture 1.Example of metal helicate

Introduction

There are four main concepts in

supramolecular chemistry to involve :
A)molecular recognition representing
selective interaction between two/three
components
B)selforganisation-connected with
systems which can spontaniously
generate well defined supramolecular
arhitecture from specific part of initial
components under specific conditions

Introduction

C)selfarrangement-responds to basic
level in selforganisation process
D)supramolecular programing
responds to involving orders in
component of any device if a device is
a metal complex

Specifity of metal helicates

Selfarrangement have been additionaly

described by Lawrence,Jaing and Levett
Stoddard et al. have defined three most
important facts of metal helicates :
a)helicity in metal helicates
b)physical and chemical parametres which
control termodynamic selfarrangement
which lead to creating helicates
c)structural characterisation of those
gigantic compounds

Specifity of metal helicates

There are some main examples of
those compounds-pseudotetrahedral
compounds with two bidentatic ligands
type AB which are coordinated on
metal center (Picture 2.a) and 2.b))*
*galium atom in picture is just for
presentation, does not represent galium
metal complex

Specifity of metal helicates

Picture 2.a) and 2.b.)A and B represents different ligands

Mechanical aspects of metal

helicates final definition

Metal helicates is a supramolecular

complex made by one or two covalent
organic straind wraped around complex
and coordinated series of ions who
have their own position in structure of
helicoidal axes

Mechanical aspects of
metal helicates

Mechanical aspects of metal helicates

needs these conditions to be aquired:
A)one or more acyclic ligands have
been wraped and coordinated around
cations or anions with forming
coordinative bond(coordinative bondold chemical definiton for chemical
interaction)

Mechanical aspects of
metal helicates

B) a helicate consists of minimal two

ions and the number n is a number
determing nucleicity and makes a
polynuclear oligomere

Mechanical aspects of metal

helicates structural effects

Metal cations are used for snythesis of

metal helicates cause they possess
specific properties needed for
supramolecular structures:
A)specific coordinative properties,
coordination numbers,stereochemical
preferences depended by size, charge
and electronic structure

Mechanical aspects of metal

helicates structural effects

B)wide spread of bond with ligands and

kinetical stability , for example:lowspin
Ru(II) and Os(II) have d8 configuration
which makes them suitable for making
inert and strong covalent bonds while
labile and weak electrostatic bonds are
made by Na(I) complexes
c)variable affinity for different bond
units-ligands

Mechanical aspects of metal

helicates structural effects

d)specific magnetic , electronic and

spectroscopic properties which can be
found in final product

Mechanical aspects of metal

helicates structural effects
Ligand properties are important :
Homotopic helicates-made from
coordinated ligand strands which possess
sequence of similar bonding unit along with
the strand with similar intrinsic informations
Heterotopic helicates-coordinated ligands
with different bonding units giving
directionality within the strand possess
two forms :Head-to-head(HH) or Head-totail(HT)

Mechanical aspects of metal

helicates structural effects

Picture 3.Homotopic helicates saturated(middle) and

unsaturated (below)(ACD chemsketch)

Mechanical aspects of metal

helicates structural effects

Picture 3.Heterotopic helicates saturated(middle)

and unsaturated (below)(ACD chemsketch)

Mechanical aspects of metal

helicates structural effects

Saturated homotopic helicateexample(ACD Chemsketch)

Kinetical aspects of metal

helicates

Reactions between metal helicates and

ligand strands match into a category
which Lindsey called as `hard
selforganised` in which final metal
helicate responds to termodinamically
most stable product
The final product requires several
conditions including bond making and
breaking

Kinetical aspects of metal

helicates

Bond making and breaking have to be

very fast in according to :
A)explore potential energy of
hypersurface of combining complex which
lead to minimum of free energy (G)
B)alow to reject `mistakes`which lead to
local minimum energy which makes that
easy to combine coordinative bonds
instead of labile hydrogen bonds most
favourable

Kinetical aspects of metal

helicates

Secondary thermodynamic effects

neccecery for fomation of helicates
are:
Alosteric effects
Regulatory effects
Cooperativity effects

Kinetical aspects of metal

helicates lability vs.inert state
To choose a metal center that will
arrange in time depended chirality taking
in mind water molecule supstitution
reactions on metal center itself
The measured reusults show that the
reactions of racemisation was faster for
ligand change on water metal complexes
most common type:[M(OH2)m]n+

Kinetical aspects of metal

helicates lability vs.inert state

Williams et al. showed that

coordination of chiral oxalate anion
changes the helicity of isolated -cisCo(R-picpn)Cl2]ClO4 complex into -cis
form in hot water(Picture 4)

Kinetical aspects of metal

helicates lability vs.inert state

Picture 4.Helicate inversion with Co(II) complex

through anion exchange

Kinetical aspects of metal

helicates lability vs.inert state

Labile metal helicates coordinated with

achiral ligands show dynamic
equilibrium between right(M mark) and
left (P mark)handed (oriented) helical
structures
There are two approaches towards
programing helical structure of labile
metal helicates

Kinetical aspects of metal

helicates lability vs.inert state

They are :
A)`ligand chirality`-also defined as
chirality of additional ligand which
gives helicoidal geometry between two
enantiomeric forms
B)`complex helicity`-around metal
center responsable for activating
supramolecular helicity or coil(Picture
5)

Kinetical aspects of metal

helicates lability vs.inert state

Picture 5.On the left:`ligand chirality` and on right

`complex helicity`(with permission of
Kagakudojin,Kagaku,2004,59,70)

Kinetical aspects of metal

helicates-choice of cations?

The range of cations or anions capable

coordinating metal center on the place
organic ligand goes withing this
sequence: NO3->Cl->Br->CF3SO3- >ClO4-PF6BF4- , and sometimes we can found CF 3SO3to be bound with NO3- to metal center
Higly symetrical ligands as flourides and
hypochlorides which are often used as
noncordinative ligands often produce
amorfcicity inside helicate complex

Characterisation of
helicates using analytical
methods

Its hard to find inner crystal structure

of any helicate due to several reasons:
Most of them are very labile(can`t
make crystals without losing some
ligand strands)
Show great dynamics in solutions
Carrying positive or negative charge
and sometimes very nonactive to form
nucleus

Usage

Manipulation and investigation of their

properties led to some advances in
chemistry of materials and proved
some physical fenomena in inorganic
reaction mechanisms
Selfrecognised and programmed
supramolecular structures as LED and
OLED(organic light emitting diodes)

Usage

Twodimensional inorganic
latters,edges,intercoiled catenates and
knots
Alosteric ionophores-metal organic
complexes important for passive
transport through intermembrane
space

Conclusion

Advantages :
Consistent with principles of supramolecular
chemistry
Used for LED, OLED and other complex
inorganic structures
Disadvantages:
Lack of determing inner structure
Restricting behaviour of ligands
Sometimes very slow or imposibble
synthesis

References

Constable,E.C.,Chem.Ind.,1994,56
Lawrence, D.S.,Jiang
,T.,Levett,M.,Chem.Rew.1995,95,2229
Harris,C.M.,Mc Kenzie,E.D.,J.Chem.Soc.
(A),1969,746
Sanchez-Quesada,J.,Seel,C.,Prados,P.,de
Mendoza,J.,Jour.of Am.Chem.Soc.,1996,118,277
Mislow,K.,Chimia,1986,40,395
Lindsey,J.S.,New.J.Chem.,1991,15,153
Williams,A.F.,Piquet,C.Carina,R.in `Transition
Metals in Supramolecular chemistry`, Khawer
Academic Publishers,1994,p404
Brewster,J.H.,Topp.Curr.Chem.,1974,47,29
Piguet,C.,Bernardinelli,G.,Hopfgartner,G.,Chem.R
ev.,1997,97,2005

References

Lehn,Jean-Marie.,Science,2002,295,2400
Van der
Sluis,P.,Hezemans,A.M.F.,Kroon,J.,J.Appl
.Crystallogr.,1989,22,340,
Chambers,J.A.,Goodwin,T.J.Mulqi,M.W.,Willia
ms,P.A.,Inorg.Chim.Acta.,1983,75,241
Biscarini,P.,Kuroda,R.,Inorg.Chim.Acta.,1988
,154,209

About me-Ana-Marija
Bartolincic

For more information look at my

linked.in profile
Contact me through e-mail:
anamarija.bartolincic@yahoo.com
Faculty of Science-Zagreb, Croatia,
section:Inorganic and Organic
Chemistry ,-subsection:complex
MOF(metal organic frameworks)and
POC (porous organic cages)