Coordination polymer polymer metal complexes research chem620 finaly-awad albalwi

Coordination Polymer &Polymer-Metal Complexes: Synthesis, Characterization, and Properties Page 1

Coordination polymer &Polymer-metal

complexes: Synthesis, characterization, and

properties

____________________________________________________________________

By

Awad Nasser Al-Balawi

Department of Chemistry

King Saud University

December,2013


Contents

Subject Page

N0# Cover -

Contents 2

1-Introduction 1-1 polymer-metal complex

1-2 Classification of polymeric metal complexes

4-7

2- Synthesis of Coordination Polymers and polymer-metal complexes 2-1. Synthesis of Coordination Polymers 2-1-1Polymerization through pre-formed metal complexes 2-1-2Coordination of a metal ion by a pre-formed polymer containing chelating groups 2-1-3.Coordination reaction of a ligand, which can attach itself simultaneously to two metal atoms or ions 2-2- Synthesis of polymer-metal complexes: 2-2-1 Complexation polymeric ligand with metal ion 2-2-1-1 Pendant complexes 2-2-1-2 Inter and Intra molecular bridging 2-3-Polymerisation of monomeric metal complexes 2-4 Complication of bi functional ligands with metal ion Example.1-Synthesis and Characterization of Polymer Metal Complexes poly-[DHPF-M(II)Cl2] which is used as Catalytic Activity in Ethylene Oligomerization Example.2- Synthesis of polymer–copper(II) complex. Example.3- Synthesis of oligo-2-[4-iodophenylimino) methyl ] phenol-metal complexes Example.4-Synthesis of the monomers and four polymeric metal complexes (P1–P4).

5-22

4-Chemical Modification of polymer metal complexes Functionalised polymers and their metal complexes: Synthetic and characterisational aspects

23-30


Subject Page N0#

5-Physical and chemical properties of polymer metal complexes

5-1- XRD analysis:

5-2- Fourier transform-infrared spectroscopy (FT-IR) 5-3-Thermogravimetric Analysis.

5- 4-Electrical properties 5-5-Optical properties

5-6- Electrochemical properties 5-7-Elemental analysis: 5-8-Magnetic measurements

5-9- Thermal analyses 5-10-NMR spectroscopy

31-38

6-Applications of polymer metal complexes 6-1-Catalytic Activities of Polymer-metal Complexes 6-2-Mechanochemical Systems 6-3-Biologically Important Polymer-Metal Complexes 6-4- Biomedical applications (Anti-bacterial activity and Anti-fungal activity) 6-5- Polymeric Ligands in Metal Ion Separations 6-6-Solar Energy 6-7 Semi conductivity

39-44

Acknowledgment 45

References 46-50


1-Introduction Over the last several decades, polymer–metal complexes have gained increasing

scientific interest for their effectiveness in various fields .

Polymeric materials with the ability to create complexes with metal ions are very

common, originating from both natural and synthetic sources [1-2]. Recent progress

made in design and synthesis of novel coordination polymers has brought a variety of

polymeric materials that exhibit the structural diversities and attractive properties

which can be further utilized in various fields, like in catalysis [3-4], organic synthesis

[5], wastewater treatment, polymer drug graft, recovery of trace metal ions 6], and

antimicrobial activities [7,8 ]. , optics, luminescence and sensor technology [9] .

A polymer-metal complex is a coordination complex between a ligand functional

group anchored to a polymer matrix and a metal ion, in which the metal ion is

attached to the polymeric ligand by a coordinate bond. The synthesis of a polymer-

metal complex can take place by the synthesis of a macromolecular ligand followed

by the binding of the metal salts which involves different processes, such as

complexation, coordination, ion exchange and electrostatic attraction or by the

incorporation of a metal by polymerization of a suitable metal containing

monomer [10]

Voges et al . reported the free radical polymerization of vinyl monomers containing

transition-metal ions[11] . Tomono et al. [12] reported the radical polymerization of Cu-

complex with Schiff base ligand containing vinyl group . Free radical polymerization

of methacrylate monomers coordinated to Co (III) complexes was reported by Osada

et al . [13] . Kurimara et al . [14] prepared a series of pendant-type polymer-metal

complexes having a uniform structure by the substitution reaction between a polymer

ligand and a metal ion, such as Co (III) or Cr (III) . Dingman et al . [15] studied the


adsorption of metal ions on poly (ethyleneimine) crosslinkcd with toluene

diisocyanate and reported that the amount of metal ions adsorbed decreases with an

increase in the degree of crosslinking. Here the synthesis and characterization of poly

(2-hydroxy-4-acryloyloxy acetophenone formaldehyde) and its Cu (II) and Ni (II)

complexes, are reported.[16]

The free radical polymerization of Cu complexes with a Schiff’s base ligand

containing a vinyl group and the radical polymerization of methacrylate monomers

coordinated to Co(III) were studied by Kaliyappan et al. [6]. Polymers that contain

nitrogen as donor atoms were synthesized and used in the complexation of transition

metal cations [17]. Among these polymers,4-vinylpyridine (4-VP) is considered

strongly functional [18].

1-1-polymer-metal complex

A polymer-metal complex is a coordination complex between a ligand function

anchored on a polymer matrix and a metal ion in which the metal ion is attached to

the polymeric ligand by a coordinate bond. Here a polymeric ligand is considered as a

polymeric substance that contains coordinating groups or atoms mainly N,O and S.

The polymeric ligand can be obtained by the polymerization of monomers containing

coordinating sites or by the reaction between a polymer and a low-molecular weight

compound having coordinating ability. 1n a polymer-metal complex, a complex with

a specific structure results since the metal ion is surrounded by a structured polymer

chain. Polymer-metal complexes show unique properties which are distinctly different

from their low- molecular weight analogues. These unique properties originate from

the properties of the polymer backbone.


1-2-Classification of polymeric metal complexes

The polymeric metal complexes are classified into the following groups:

(A) polymer-metal complexes

(B) coordinate polymers

(C) poly(metal-phthalocyanine) type

Polymer-metal complexes, represented by Schemes 1 to 5, are defined as complexes

composed of a polymer ligand and metal ions in which the metal ions are attached to


the polymer ligand by a coordinate bond. Here a polymer ligand is understood to be a

polymeric substance that contains coordinating groups or atoms (mainly N, O, and S),

obtained by the polymerization of monomers containing coordinating sites, or by the

chemical reaction between a polymer and a low-molecular- weight compound having

coordinating ability Typical polymer ligands previously reported are listed in Table I.

When a polymer ligand is mixed directly with a metal ion, which generally has four or

six coordinate bonding hands, a polymer-metal complex is formed. This may be of the

intra-polymer chelate type (Scheme 1) or of the inter-polymer chelate type (Scheme

2). Complex formation proceeds via Scheme 3, where the polymer backbone contains

multidentate ligands, such as the iminodiacetic acid group, or acts as a carrier for low-

molecular-weight mu!tidentate ligands; many so-called chelating resins fit this

scheme. The polymer-metal complexes represented by Schemes 1 to 3 have chelating

structures in their polymer ligands and are therefore called polymer chelates. The

pendant-type polymer-metal complex (Scheme 4) is formed by the reaction of a

polymer ligand with a stable metal complex, the central metal ion of which has

already been masked with lowmolecular- weight ligands except for one coordinate

site that remains vacant, e.g. metalloporphyrins, or cobaltic chelates. A polymer-metal

complex is also obtained by polymerizing a monomeric metal complex (Scheme 5).

Scheme 6 represents coordinate polymers. A low.molecular-weight compound with

multidentate groups on both ends of the molecule grows into a linear polymer with

metal ions, and the polymer chain is composed of coordinate bonds. The parquet like

polymer complexes, poly(metal-phthalocyanine) and poly(metal-tetracyanoethylene),

are classified into Scheme 7. They are formed by inserting metal ions into planar-

network polymers or by causing a low.molecular-weight ligand derivative to react

with a metal salt and a condensation reagent.


2- Synthesis of Coordination Polymers and polymer-metal complexes

2-1. Synthesis of Coordination Polymers

The literature reveals three possible methods of preparing metal coordination

polymers (Marcos, 1992)[20] .

The first method involves polymerization through pre-formed metal complexes

through functional groups where the polymer forming step is typically a condensation

or an addition reaction. The second method includes the coordination of a metal ion

by a preformed polymer containing chelating groups. In the third method, a metal

coordination polymer is formed by a coordination reaction of a ligand, which can

attach itself simultaneously to two metal atoms or ions (Ismet, 2008).[21]

In theory and in practice, a myriad of ligands can be employed for such procedures.

This can be seen as a means through which various architectures can be produced

covering a wide circle of many metal atoms and ions. Some typical ligands are

displayed in table 1.

Table 1: Some ligand groups with examples, typically used in the synthesis of metal

containing polymers (Batten et al., 2008)[22 ].

Ligands bind metal atoms mainly through nitrogen or oxygen where the binding

modes affect the conformation of the metal containing polymers. Figure 1 shows a

number of binding functional groups through which the ligands bond the central metal

atoms or ions.

Ligand class Example(s)

Amides 4-(methylamino)benzoic acid

Carboxylate based Acetate, Carboxylate

Nitrile based Nitrile based 1,3,5-tris(4-ethynylbenzonitrile) benzene, 1,3,5-tris(3-

Pseudohalide Cyanide, Azide

Sulfonate containing 4-sulfo-benzoate, , naphthalene-1,5-disulfonate

5 membered heterocyclic Pyrazole, Triazole

6 membered heterocyclic Pyrazine, Piperazine, Pyrimidine


1- Polymerization through pre-formed metal complexes

In this concept, a metal complex is prepared from the reaction of a ligand with a metal

ion. The prepared metal complex is then polymerized through the various

polymerization reaction mechanisms. This is as reported by Irina (2008)[23], on the

synthesis and electro optical properties of metal-containing azopolymers and the

influence of steric factors on the electro-optical effect in poly complexes of

azobenzene derivatives with Cobalt. The synthesis was achieved by first, synthesizing

the azo compounds 4-hydroxy-(4’-carboxy-30-hydroxy)-azobenzene and 4-hydroxy-

(2’-carboxy)-azobenzene. The synthetic route for the target monomers is shown by

schemes 9 and 10. Complexes of 4-methacroyloxy-(40-carboxy-30-hydroxy)-

azobenzene and 4-methacroyloxy-(20-carboxy)-azobenzene with Cobalt were

synthesized by the exchange reaction between acetates of the corresponding metal and

monomers. The polymers were finally obtained by free-radical polymerization with

AIBN as free radical initiator. The polymers show photoinduced optical anisotropy

which is as a result of irradiation by linearly polarized light, which causes trans-cis


isomerization of azobenzene groups. There was an orientation of the light-induced

dipole moments of these groups by an external electric field, causing the electro-optic

effect at wavelengths near the long-wave absorption edge of the polymers.

Scheme 9: Synthesis of 4-methacroyloxy-(40-carboxy-30-hydroxy)-azobenzene

Scheme 10: Synthesis of 4-methacroyloxy-(20-carboxy)-azobenzene[52]

Shagisultanova (1996)[24] reported the synthesis and properties of photoactive and

electroactive polymers based on transition metal complexes. Electrochemical


reduction of iron, ruthenium and osmium complexes containing 5-Cl- Phen as ligand

leads to the growth of metallopolymers on the metal surface. The polymers were

found to be very stable to repeated electrochemical cycling and were highly

reproducible.

2- Coordination of a metal ion by a pre-formed polymer containing chelating

groups

In this aspect, a polymer is formed by any of the conventional polymerization

mechanisms. The pre-formed polymer, containing chelating groups is then

coordinated to the metal ion. This was demonstrated by Weilin et al (2003)[25] who

worked on the synthesis and ferromagnetic property of Bithiazole based polymer and

its ferro complex containing hexacyanoferrate (III) group.

The polymer (referred to as SDP) was prepared according to the reaction scheme 3.

The precipitate thus produced was collected by suction filtration, followed by washing

successively with water, methanol, and ether and dried in vacuo at 60◦C for 24hrs to

give a yellowish-green powder (yield 90%). Ferro-Complex (SDP-Fe2+) was prepared

from the reaction of SDP and FeSO4 in DMSO for 5 days at room temperature under

a purified nitrogen atmosphere. SDP-Prussian blue complex was prepared from

reaction of K3[Fe(CN)6] in DMSO with SDP-Fe2+ complex and the resulting

suspension was allowed to react for 3 days at room temperature. Elemental analysis

yields the formula [C15H12N4O3S2 (FeSO4) 0.23]n and

{C15H12N4O3S2[KFeFe(CN)6]0.20}n for both complexes. The presence of

ferromagnetic coupling between iron ions through cyano bridging linkage in SDP-

Prussian blue is proposed based on the electron spin resonance spectroscopy (ESR).


Scheme 3: Synthetic route of SDP, SDP-Fe2+ and SDP-Prussian blue and suggested structures.

Vaishali (2006) reported the Preparation, characterization, magnetic and thermal

studies of some chelate polymers of first series transition metal ions. A modified

method (Priyadarshini and Tandon, 1967)[49] based on Schotten Baumann reaction

was used for the preparation of hydroxamic acid (Ukey, 2006)[50]. The chelate

polymers were prepared according to the procedure described by (Ukey, 2006)[60].

Figure 12 shows the proposed structure of the chelate polymers. On the basis of

elemental analyses, infrared (IR) spectra, reflectance spectra, magnetic moment data

and thermal studies, the [Zn(II)(ABHA)]n chelate polymers have tetrahedral

Fig 11


geometry, whereas [Mn(II)(ABHA)(H2O)2]n, {[Ni(II)(ABHA)-(H2O)2]·(H2O)}n and

{[Co(II)(ABHA)(H2O)2]·(H2O)}n chelate polymers have octahedral geometry and

order of reactions has been found to be approximately one and have thermal stability

in the order Ni(II) > Mn(II) > Zn(II) > Co(II).

Figure 2: Proposed structure of the chelate polymers of azelaoyl-bis-hydroxamic acid,

where *H2O-water of hydration and H2O-water of coordination. M= metal ion,

Mn(II), Co(II), Ni(II) and Zn(II). *H2O is absent in case of Mn(II) ABHA chelate.

Both H2O and *H2O molecules are absent in the case of Zn(II) ABHA chelate

polymer.

3- Coordination reaction of a ligand, which can attach itself simultaneously

to two metal atoms or ions.

Coordination polymers and oligomers containing dimetal clusters have not been

explored as much as other coordination polymers, although numerous bridgded

dimetal units containing copper, rhodium, molybdenum and ruthenium are known

Fig12


(Craig, 2002)[51] and recently, two reviews describing examples of dimetal

tetracarboxylate unit containing one-dimensional polymers appeared (Craig, 2002)[51]

211]. Tetrakis(carboxylato) rhodium compounds were first reported in 1960. The

preparation of the polymers was achieved by the use of metal containing building

block with free donor sites which can be joined together through the free binding sites

to form many repeating units (polymers).

Reported by Craig (2002)[51] is the synthesis of a new mixed-metal Mn–Rh

coordination polymer assembled from Mncontaining molecular building blocks and

Rh2(OAc)4 dimers. The starting material Mn(2-methylpyrazine-5-

carboxylato)2(H2O)2, was synthesized by reacting 2-methylpyrazine-5-carboxylic

acid with MnCl2- 6H2O in a basic solution. It was then reacted further with

Rh2(OAc)4 by layering the two reactants in methanol and ethanol, respectively which

yielded small red block crystals. Single crystal X-ray diffraction revealed the red

crystals to be a new mixed-metal manganese/rhodium coordination polymer

{[Mn(MePyzca)2(MeOH)2][Rh2(OAc)4]} 2MeOH. This new manganese–rhodium

mixed metal coordination polymer complements other known systems based on the 2-

pyrazinecarboxylate and 2-methylpyrazine-5-carboxylate ligands. In all cases, the

ligand chelates one metal center with a carboxylate oxygen and one nitrogen donor

while using the para nitrogens to bind a second metal.[52]


Fig.13

Fig.14


2-2- Synthesis of polymer-metal complexes:

2-2-1 Complexation polymeric ligand with metal ion

This type of complex formation is achieved by mixing a polymer containing

ligand functions like amine, ketone, dithiocarbamate, carboxyljc acid, thiol, schiff

base . with metal Ion or metal complex solution. The reaction usually resulted in

various types of co-ordination structures like pendant, inter and intramolecular

bridged complexes.( Chacko - 2010 )[20]

2-2-1-1 Pendant complexes

a metal ion or metal complex has only one labile ligand which is easily substituted

by a polymeric ligand and when other co-ordination sites are substituted by a

polymeric ligands and other coordination sites are substitution inactive. a

amonodentate pendant complex is formed.

The polymer complex cis [Co(en)zPVP.CI]C12 was prepared by mixing an

ethanolic solution of PVP with an aqueous solution of Co(1ll) chelates and heating

at 80°C for 2-6 h. The solution was filtered and the filtrate was dialysed in cold

water. After the water was evaporated thin films of reddish violet PVP complex

was obtained.

A polymeric ligand having polydentate structure will form polydentate

pendant complexes.


2-2-1-2 Inter and Intra molecular bridging

The reaction of a polymer ligand with metal ions very often results in inter and /or

intramolecular bridging.

2-2-Polymerisation of monomric metal complexes

If a monomeric metal complex containing a vinyl group is polymerized without

side reaction, a polymer metal complex having uniform structure is obtained.


Typical example of the polymerization of a vinyl monomer containing translation

metal ion is the radical polymerization of vinyl ferrocene. Vinyl t'errocene and its

derivatives are polyrmerised by a radical or cationic initiator to atom a polymer of

high molecular weight. Methacrylate monomer coordinated to Co(III) complex eg.

methacrylate pentamine Co(III) perchlorate was radically perchlorate was radically

polymerised get the polymer metal complex. (Chacko - 2010) [20]

Complication of bi functional ligands with metal ion

When bifunctional ligands form a complex with metal Ions having more

than two labile ligands which are easy to be substituted a polymer complex IS

formed through metal Ion bridging . this type of polymer metal complex has been

used as semiconducting organic materials, heat resistant organic copolymers or

polymer catalysts .


Example.1-Synthesis and Characterization of Polymer Metal Complexes poly-

[DHPF-M(II)Cl2] which is used as Catalytic Activity in Ethylene

Oligomerization

Ahamad and ALshehri 2013, reported a new polymeric ligand, 4,7-dihydroxy-1,10-

phenanthroline/formaldehyde polymeric ligand [poly-(DHPF)], which was

synthesized via the polycondensation of 4,7-dihydroxy-1,10-phenanthroline and

formaldehyde in an acidic medium. Polymer metal complexes, poly-[DHPF-

M(II)Cl2], were subsequently prepared with Co(II) and Ni(II) ions. Poly-(DHPF) was

prepared through the condensation polymerization of formaldehyde and 4,7-

dihydroxy-1,10- phenanthroline in an acidic medium. Polymer metal complexes were

prepared upon the reaction with metal salts, using a 1:1 molar ratio of polymeric

ligand to metal. The synthetic routes for both the polymeric ligand and its polymer

metal complexes are given in Scheme 15. The poly-([DHPF-Co(II)Cl2]) was isolated

as a blue powder, whereas poly-([DHPF-Ni(II)Cl2]) was green. Slight deviations in

the elemental analysis may be due to the polymeric nature of the compounds, as the

values for the end groups are not taken into account for the theoretical calculation. [21]

Scheme15


Example.2- Synthesis of polymer–copper(II) complex.

Cao et al 2013 & Tsuchida et al 1977 reported method for Synthesis of polymer–

copper(II) complex (fig). the water-insoluble polymer–copper(II) complex was

synthesized in supercritical carbon dioxide by using methanol as a cosolvent and N,N-

methylenebisacrylamide as a cross-linker. In a normal reaction, three basic steps are

performed to synthesize the polymer–copper (II) complex. First, copper sulfate and

4-VP are used as the coordination ion and the functional monomer, respectively,

Second, a free-radical initiator (AIBN), a cross-linker (BISl), and an appropriate

is then immediately 2the autoclave. CO amount of methanol are loaded into

introduced . Third, the system is isolated, and the autoclave is placed in a water bath.

In addition, the reagents are mixed and dissolved before heating the reaction system to

]22,23[.( scheme16) temperaturethe reaction

Scheme.16


Example.3- Synthesis of oligo-2-[4-iodophenylimino) methyl ] phenol-metal

complexes

Kaya & Baycan 2007 reported synthesis Polymer–metal complex compounds were

synthesized from the reactions of poly-2-[(4-mercaptophenyl) imino methyl] phenol

(P-4-MPIMP) with Cr3+, Co2+, Ni2+, Cu2+, Mn2+, Zn2+, Pb2+, Cd2+ and Zr4+ ions.[25]

Oligomer-metal complexes were synthesized from the reactions of OIPIMP(2-[(4-

iodophenylimino)methyl]phenol with Co(II), Ni(II) and Cu(II) acetates. As shown in

the Scheme 18.

Scheme17

Scheme.18


Example.4-Synthesis of the monomers and four polymeric metal complexes (P1–P4).

Jin et al2013 reported Four main chain polymeric metal complexes (P1–P4) based on

1,10-phenanthroline metal complexes via the Heck coupling have been synthesized

Schem.19. [26]

Scheme 19. Synthesis of the monomers and four polymeric metal complexes (P1–P4).


4-Chemical Modification of polymer metal complexes

4-1-Functionalised polymers and their metal complexes: Synthetic and

characterisational aspects

In 1963, Merrifield introduced the concept of solid phase peptide synthesis,

after which solid polymer supports were used extensively in other areas of

chemistry ' The advantages of solid phase reactions are the operational simplicity,

possibility of using one of the reagents in excess, and the ease of purification.

Polymer supports have gained wide application not only in solid phase peptide'

synthesis but also in different areas like immobilisation of enzymes, biomolecules,

catalysts, reagents and in metal ions separation.

The polymer support should be functionalised before exploiting them for chemical

processes like peptide synthesis, catalysis, chelation or metal ion separation.

Functionalisation involves the incorporation of a functional group to the polymer

support.

Chloromethyl polystyrene crosslinked with 1-2% divinyl benzene is the

most commonly used support. Functionalisation of styrene polymers primarily

involves electrophilic substitution on the aromatic ring. Chloromethylation has

been the most widely used reaction. Chloromethylation of styrene polymers is

carried out using a Lewls acid catalyst and chloromethyl methyl ether as the solvent.

In addition to their direct use, chloromethyl groups can be readily modified into

other functional groups Different functional groups may be directly introduced

into the polystyrene support by well known reaction sequences .

Several ligand functions were anchored to polymer support by polymer

analogous reactions to get polymer supported ligands. These polymer supported

complexing agents find wide application in various fields.


a- incorporation of ligand,

Two approaches exist for the preparation of functional polymers, namely the

polymerization or copolymerization of monomers which carry the desired

functionality and the chemical modification of the preformed polymer. The

tormer is the more direct approach and many functional linear polymers can be

prepared without difficulty by free radical, anionic, cationic, co-ordination or

group transfer polymerization . However for most purposes cross-linked polymers

are more attractive than linear polymers. The preparation of crosslinked polymers

in a good physical form is most readily achieved by suspension polymerization.

The alternative to direct copolymerization for the preparation of functionalized

polymers is the chemical modification of preformed polymers.

'This method is preferred to others in view of the fact that the degree of

functionalisation can be controlled by varying the amount of crosslinking agents

and the extent of modification in preformed matrices. The method involving

copolymerization of monomers controlling the desired functionality's widely used

to produce Ion exchange and complexings sorbents.

Vinyl monomers are usually used and the synthesis involves the polymerization of &

of vinyl compounds containing chelating groups like pyridine, 8-hydroxyquinoline,

Imidazole carboxylic acid etc. with divinyl compound .Yeh et al . reported the

Preparation of polystyrene based acetyl acetone by direct emulsion polymerization

of a vinyl benzyl acetyl acetone with styrene using the conventional emulsion

system or by bulk polymerization using azobisisobutyronitrile as solvent and by

irradiating the monomer by UV radiation. This method of synthesis makes it

possible to obtain sorbents of high capacity and a uniform structure of the polymer.


Chemical modification of the preformed polymer is the easiest method for the

Synthesis of wide variety of macromolecular ligand systems. This method is

generally used for the functionalisation of a polymer matrix. The required ligand

function is Introduced on to the polymer matrix by simple polymer analogous

organic reactions Imdazole supported on styrene divinyl benzene copolymers can

be prepared from chloromethylated styrene DVB copolymers and the sodium or

lithlum salts of imazoluesing dimethyl form amide or tetrahydrofuran as

solvent . the bidentate ligand 2,2'-bipyridine has successfully incorporated into

polystyrene by (Card and Neckers' according to Scheme.20below


Drago et al. described the strategy for covalently attaching multidentate chelating

ligands to polystyrene matrix. Polymeric substrates containing polydentate amines can

be obtained by reacting chloro or iodomethyiated polystyrene with bis

(cyanoethylamine) followed by BF,-THF reduction. Preparation of polymer attached

bis(3-aminopropyl) mine is depicted in Scheme.21 below.


Bhadurl and Khwaja synthesized some polymer supported dithiocarbamate ligand

from chloromethylated styrene divinyl benzene copolymers (8%) using the sequence

of reactions given below scheme.22.

Polycondensation is another important method for synthesizing polymers

bearing chelating ligands. This method involves the copolymerization of certain

21

22


ligand molecule with phenols and aldehydes. For example, anthranilic acid,

; anthranihc acid diacetic acid,. m-phenylene diamine can be copolymerised with

formaldehyde and mono or polyphenols to synthesize condensation chelating

polymers. Unicellex UR-50 is a chelating Ion exchange resin prepared by the

copolymerization of N-(0-hydroxybennl) imidodiacetic acid with phenol and

formaldehyde. Recently Patel et a1 prepared a polymer by condensation of 2-hydroxy

4-methoxy acetophenone and 1.4-butane diol.

The two-stage metallation of the polymer by chelate complexes of butyllithium with

subsequent functionalization of metal-containing intermediates has been employed

successfully for modification of a number of polymers, for example, polystyrene,

cis-1,4-polybutadiene,and cis -1,4-polyisoprene. Earlier, an attempt was made to

apply the same approach for functionalization of PTMSP with the use of normal

butyllithium in a polar medium and a hydrocarbon medium containing electron-donor

additives. However, the degree of metallation of the polymer by the above systems

turned out to be low. As a result, only a small amount of functional groups (not

greater than 8 mol % even when a threefold excess of the metallating agent was used)

was incorporated into PTMSP.

(Scheme (23))The metallation of PVTMS and PTMSP was performed with the use of two types of

metallating agents—normal and secondary BuLi—as chelate complexes with TMEDA.

Chirkova et al 2006 reported that Poly(vinyltrimethylsilane) and poly(1-

trimethylsilyl-1-propyne) are metallated using normal and secondary butyllithium


chelate complexes with tetramethylethylenediamine and superbases based on

complexes of normal and secondary butyllithium with potassium tert -pentoxide as

metallating agents. Poly(vinyltrimethylsilane) and poly(1-trimethylsilyl- 1-propyne)

are functionalized via reactions of metallated polymers with CO2 , trimethylsilyl

chlorosulfone, diethyl disulfide, and ethylene oxide. COOH, SO3H, OH, and thioester

groups are introduced into poly(vinyltrimethylsilane), and SO3H and COOH groups

are incorporated into poly(1-trimethylsilyl-1-propyne). Upon introduction of carboxyl

groups into poly(vinyltrimethylsilane), its hydrophilicity and permselectivity with

respect to H2O/N2, H2O/H2, and H2O/CH4 pairs increase. The introduction of SO3H

groups into poly(1-trimethylsilyl-1-propyne) and poly(vinyltrimethylsilane) leads to

the appearance of proton conductivity of these polymers.( Chirkova et al 2006)[27]

It was reported that Fullerenes, in particular C60 as one of the new materials - has

been bonded to polymer-metal complex for the first time with two methods. C60 is

directly coordinated in the side-group attached to the main chains of polymer to form

PVPy (charm Bracelt)-metal (Cu, Co, Ni ...)-C60 complex or it is, in a

anion,coordinated with the polymers. To gain Pearl Nechleace polymer, some

diamino derivatives of C60 have been synthesized. The complex with C60 can be

coated on some substrates, such as silicon, glass, alumina (AI2O3), to form the film.

The polymer-metal-C60 complex (P-M-C60) can be implanted by H+, P+,B+ , Sb+ or

metal ions to modify the complex.( Zhang et al 1995)[28]

Shunmugam, & Tew 2008 stated that the area has begun to focus considerable effort

on the properties of these materials for various applications that will move the field

from interesting molecules to ‘functional materials,’ a very promising prospect.

Nevertheless, the ability to engineer functional materials rests on the availability of


novel materials and, therefore, on advances in synthetic chemistry. Figure .24below

shows a selected summary of various structures reported to date in this area with a

focus on those used for emission properties .[29]

Scheme24


5-Physical and chemical properties of polymer metal complexes

Analysis and Characterization of Polymer-Metal Complexes

Usual chemical methods of analysis applied to low-molecular weight species have

been found to be satisfactory with linear polymers. But with crosslinked

polymers such methods which require solubilization of the samples cannot be applied.

The detection and estimation of the elements present in the polymer-complexes are

carried out by elemental analysis. The different functional groups (ligands) are

detected qualitatively by the general chemical tests and from their typical IR

absorptions. If the ligand functions supported on the polymer are acidic or basic, a

quantitative estimation of the groups can be done by titrimetric method, provided,

the support material allows penetration of the aqueous reagents. In the case of

reagents where the penetration of the aqueous reagen,ts is difficult, it is better to

react the supported group with excess of acid or base, allowing the reaction for a

sufficiently long period and then to carry out back titration. The complexed metal

ions are estimated by volumetric, spectrophotometric or gravimetric methods. The

metal ion intake is usually expressed as milligram of. metal ion complexed by one

gram of the resin.

The coordination of a polymeric ligand to metal ion and the structures of the resulting

polymer metal complexes are studied spectroscopically and by measuring the

magnetic properties. Infra-red (IR), visible, electron spin resonance(ESR), NMR,

Scanning electron microscopy(~M), X-ray, optical rotatory dispersion(ORD) and

circular dichroism(CD) can be made use of for the structure elucidation of polymer-

metal complexes.

Thermal studies (TGA/DTA) have also been used to explore composition, structure

and thermal stabilities of polymeric ligands and their metal complexes. Applications

of these methods are illustrated in the respective sections dealing with individual


chelating polymers and their metal complexes. Increasing importance is not

attached to the use of these methods as various physical measurements can help in

adequate characterization of crosslinked chelating resins to indicate the chemical

environment of the attached chelating group.

Physical and chemical properties of polymer metal complexes Can be

Characterization by several techniques as following:

5-1- XRD analysis:

The crystallinity of the polymer–metal complex often is examined by powder XRD

For example , it can explain the XRD analysis for the synthesis of Example.2-

Synthesis of polymer–copper(II) complex. Cao et al 2013 explain the fig.2 saying

that the curves indication to (a) the polymer and (b) the polymer–copper(II)

complex. the fig.25 show that there is no Cu peaks are observed in the diffractograms

of the polymer complexes of 4-VP. This result indicates that these complexes are not

composed of single crystallites . This result also indicates the absence of excess salt in

the complexed polymer. The XRD patterns of samples (a), polymer (b), and the

polymer–copper(II) complex are similar. However, the intensity of the peaks

increases after the monomer interacted with the copper ions. This behavior indicates

that the complexation between copper(II) and the polymer link, which takes place in

metal –e polymerthe polymeric network, results in an amorphous structure of th

]22, 29[complex.


Fig. 25. XRD analysis of (a) the polymer and (b) the polymer–copper(II) complex.

5-2- Fourier transform-infrared spectroscopy (FT-IR)

The FT-IR spectra of the compounds ( monitor , polymer, polymer- metal

compolexes ) can be recorded as KBr discs using FT-IR spectrophotometer .

Absorption frequencies are given in wave numbers (cm−1). FTIR bands and its

signals of monomer, its polymer-metal complexes with their assignments are can be

observed . It give indication on the present/ formation the Metal- function group

bond and other function group, in the polymer- metal complexes.

The formation of polymer metal complexes can be followed from their

characteristic absorption bands in infra-red and far infrared spectra and comparing

them with the corresponding low molecular weight complexes. The IR absorptions

by a ligand are usually shifted by complex formation with metal ions. The

absorption band at 1600 cm-1 of (C=C) or (C=N) of poly(4-vinyl pyndine), (PVP)

shifts to a higher wave number by about 20 cm-1 in cis [CO(en)2 PVP.CL]CL2

cis[Co(trien)PVPC]CL the (C=C) and (CH) of PVP also shift to higher wave

number in the Co(I1I) complex. When two kinds of ligands capable of coordination

are present in the polymer, the IR spectra can be used to find out the group which

participates in co-ordination .( Chacko - 2010 )[20]


5-3-Thermogravimetric Analysis.

The thermal decomposition of polymer , and its polymer metal complex can be

studied by the thermogravimetric method. The thermogravimetric curves of polymer

and its polymer metal complex give indication on starting decomposing with weight

loss at certain temperature as a result in some cases of related to the volatilization

of both water and plasticizer . For example , it can explain the Thermogravimetric

Analysis related to the synthesis of Example.2- Synthesis of polymer–copper(II)

complex. Cao et al 2013 explain fig.3 saying that The TGA curves of cross-linked

P(4-VP) (a) and of the polymer–copper(II) complex (b) are shown in Fig. 26. The

starting volatilization temperature of the polymer complexes was about 315 ◦C, which

indicates that the polymer complexes are less stable than the PVP homopolymer.the

decomposition temperature of the cross-linked P(4-VP) is at 374 ◦C, whereinthe

polymer–copper(II) complex separated into two segments,

namely, at 315 ◦C and 515 ◦C.


5- 4-Electrical properties Electrical properties of doped and undoped polymer and polymer–metal complex

compounds can be determined by four point probe technique at room temperature

and atmospheric pressure using conductivity instrument . The pellets are pressed on

hydraulic press developing up to 1687.2 kg/cm2. Iodine doping is carried out by

exposure of the pellets to iodine vapor at atmospheric pressure and room temperature

in a desiccator , This discretion is according to reports by ( Diaz et al 1999 , Kaya &

Baycan. 2007) [30,24]

5-5-Optical properties

The optical band gaps (Eg) of monomer, polymer and its polymer–metal complex

compounds can be calculated from their absorption edges. Ultraviolet–visible (UV–

vis) spectra can be measured by (UV–vis) instrument . The absorption spectra of

monomer, polymer and polymer–metal complexes can be recorded by using methanol

Fig.26


and DMSO, respectively, at 25 ◦C . this method reported by (Wanger et al 2002)[31].

5-6- Electrochemical properties:

Cyclic voltammetry (CV) measurements usually carriy out with Electrochemical

Analyzer Instruments, at a potential scan rate of 20 mV/s. All the experiments are

performed in dry box under Ar atmosphere at room temperature. The electrochemical

potential of Ag is calibrated with respect to the ferrocene/ferrocenium (Fc/Fc+)

couple. The half-wave potential (E1/2) of (Fc/Fc+) is measured in 0.1 mol/L

tetrabutylammonium hexafluorophosphate (TBAPF6) acetonitrile solution is 0.39V

versus Ag wire or 0.38V versus saturated calomel electrolyte (SCE). The

voltammetric measurements are carried out for monomer, polymer and polymer–

metal complexes in acetonitrile and DMSO, respectively. The HOMO and LUMO

energy levels of the polymer and polymer–metal complexes are determined from the

onset potentials of the n-doping (φn ) and p-doping (φp), respectively, this method

was used for 4-MPIMP and P-4-MPIMP which reported by (Colladet etal 2004 & Li

et al 1999) [32,33].

It was reported The highest occupied molecular orbital (HOMO) and lowest

unoccupied molecular orbital (LUMO) energy levels of the polymer metal complexes

, which are crucial property for materials used , can be estimated by cyclic

voltammogram (CV). When saturated calomel electrode electrode was used as the

reference electrode, the HOMO, LUMO, and energy gap (Eg) can be calculated

according to Equations (1), (2), and (3), respectively, following the literature.[34]


5-7-Elemental analysis:

Carbon, hydrogen, nitrogen and sulfur contents often performe via elemental analyzer

.Analysis of metal ions after the dissolution of the solid complex in hot concentrated

nitric acid, HNO3, then diluting with distilled water and filtering to remove the

precipitated polymer ligand. The solution then is neutralized with ammonia solution

and the metal ions are then titrated with EDTA ,this method reported by(Vogel, 1978;

West, 1969).[35,36]

5-8-Magnetic measurements:

Magnetic susceptibilities of the complexes were measured by the Gouy method at

room temperature using a magnetic susceptibility balance .. Effective magnetic

moments were calculated from the expression µeff = 2.828 (XMT)1/2 B.M., where XM is

the molar susceptibility corrected using Pascal’s constants for the diamagnetism of all

atoms in the compounds and T is the absolute temperature (Mabbs & Machin,

1973).[37]

5-9- Thermal analyses :

The thermal degradations of monomer ,polymer polymer – metal complexes can be

studied by TGA– DTG–DTA analyses at N2 medium and thermal analyses results and

the curves of these analyses can be given as curves . such higher resistance against

high temperature of monomer and polymer and polymer metal complexes can be


explained base on the formation bonds between atoms. For example , high of thermal

stability of polymer–metal complex compounds may be indicate the formation of

metal–oxygen and metal–nitrogen coordination bond between polymer–metal ions.

The presence of water can be seen in TGA and DTG curves of polymer–metal

complex compounds . method of detecting glass transition temperatures can be

recorded by DTA and DSC . this method reported by (Cazacu et al 2004)[38]

5-10-NMR spectroscopy

NMR spectroscopy has also been used to study polymeric compounds 1H 13C and I9F

NMR spectroscopy were used In monitoring solid phase reactions 13C NMR

spectroscopy is used nowadays as a powerful spectroscopic method for the study of

cross-linked polymers .

The 1H NMR spectra for poly-ligand further support the characterization, as shown in

Evidence for the polymerization monomer and also give indications for

disappearance of the signals assigned to the cirtain protons. Coordination to the metal

ions is indicated by the expected upfield shifts (1H NMR) for the signals of protons.

In the 13C NMR spectra of poly and poly-Metal can be studied , for example . the

appearance of resonance signals for the CH2 groups & other group ( C-OH CH= N)

can a strong evidence for the presence of these groups in polymeric ligand and metal

complex,


6-Applications of polymer metal complexes

The study of the polymer-metal complexes has received increased interest recently in

various branches of chemistry, chemical technology and biology and the subject has

been reviewed. periodically The chelating polymers find application in collecting

transition metal ions as well as alkali and alkaline earth metal ion preconcentration

and recovery of trace metal ions , organic synthesis ', nuclear chemistry, water- and

waste water-treatment , pollution control, industrial processes , hydrometallurgy and

polymer drug grafts . In addition , polymer-metal complexes are also used as

mechanochemical systems and as models of bioinorganic systems

6-1-Catalytic Activities of Polymer-metal Complexes

Catalytically active polymers can be obtained by introducing a catalytic centre to a

polymer backbone and it is reasonable to assume that the catalyst bound to the

polymer will show specific catalytic activity, reflecting the properties of polymer

chain. In the case of metalloenzyme such as oxidase and haemoglobin where a metal

complex is the active site, the macromolecular protein is that which plays a significant

role. Polymeric catalyst reduces the possibility of catalyst poisoning since the atalytic

site is somehow protected by the polymer matrix. In a polymer-metal complex,

aggregation is physically prevented by the rigidity of the polymer matrix and has the

advantage of maintaining its catalytic activity over a wide range of concentration. In

polymer-metal complexes, the selectivity arises from the steric hindrance and/or

chemical environment of the polymer matrix." Polymer-metal complexes are

markedly useful as immobilised catalyst for practical use because it is more reactive

than the corresponding monomer analogous due to the specificities of their large

ligand molecules. It is mainly used in oxidations, hydrogenation hydrolysis,

hydrformylation , decomposion of H2O2, " initiation of radical polymerisation,


asymmetric synthesis and optical resolution.

There are only a few examples where such polymer metal complexes act as catalysts,

which include epoxidation, hydrosilylation, hydroformylation, and hydrolysis. A vast

number of N-heterocyclic organometallic compounds have been applied toward the

polymerization of ethylene owing to their low cost, low toxicity, and abundance,

rendering them versatile precursors. It was reported of synthesis of a 4,7-

dihydroxy-1,10-phenanthroline/formaldehyde polymeric ligand [poly-(DHPF] in an

acidic medium and its subsequent Co(II) and Ni(II) polymer complexes, poly-

([DHPF-Co(II)Cl2] and poly-([DHPF-Ni(II)Cl2]), respectively. In addition ,their

catalytic activities have been assessed under a range of conditions toward ethylene

oligomerization. (Ahamad and Alshehri 2013)[39]

6-2-Mechanochemical Systems

mechanochemical system is one which can convert chemical energy into mechanical

change which results in the deformation of the materials. A polyelectrolyte or a

polymer-metal complex acts as a sensor in a mechanochemical system. The addition

of Cu(II) ions to the filaments of poly(viny1 alcohol) dipped in an aqueous solution

caused a shrinkage of filamentsg5. The film is extended by about 20% on the

reduction of Cu(II) to Cu(I) and shrinks back to its original state on the oxidation of


Cu(1) to Cu(I1). The poly(viny1 alcohol) chain is densely crosslinked by the

extremely stable Cu(II) chelate but is loosened when Cu(II) forms the unstable CU(I)

chelate.

Mechanism of Mechanochemical change of PVA Filament Induced by Redox

Reaction of Ions

The viscosity of an aqueous solution of poly(viny1 amine) in the presence of Cu(II),

Ni(II) or Zn(I1) ions was sharply changed by changing the pH of the solution due to

the conformational change of the polymer The mechanochemical behaviour caused by

pH change is less than the change caused by the redox reaction of the complexed

metal ions .

6-3-Biologically Important Polymer-Metal Complexes

Metal ions have an important role in the activity of bioinorganic materials in which

metal Ions are bound to proteins, nucleic acids and related ligands.

Here the metal ions are bound to huge polymeric ligands and give rise to

characteristic properties which are different from those of the corresponding low-

molecular weight analogues. a. Complex Formation of Metal Ions with Biopolymers

6-3-1 Metal complexes of Polypeptides

Metalloenzymes are generally formed between a polypeptide and metal ion. The

coordination structure of the complex, the conformation of the polypeptide which

is dependent on the sequence of the amino acids in the polypeptide, stiffness of the

backbone and the interaction between the pendent groups cause specificities in

metalloenzymes . The onset of coordination in polypeptides is generally by the

presence of sulphur, nltrogen and oxygen in various functional groups. The

coordination structures of the Cu(II) complexes of synthetic poly(amino acid)s are

generally dependent on the pH of the solution. Mainly these complexes are planar

or distorted planar. The coordination of poly(Lhistidine) with Cu(II) ions gave a


square-planar structure at pH 5. This square-planar complex is formed by the

coordination of three imidazolyl groups of histidine and one peptide nitrogen on the

main chain. At pH 14, a distorted square-planar structure is formed by

the coordination of four neighbouring peptide nitrogens with one imidazolyl group

coordinated at an apical position .

6-3-2 Metal Complexes of Nucleic Acids and Related Compounds

Due to the presence of negatively charged phosphate groups in RNA and DNA, their

structure can be stabilized only in the presence of positive charges like metal ions or

organic cations. The role of metal ions is to maintain higher structure or to participiate

in the replication, transcription or translation of DNA. Metal ions cause the

denaturation of DNA or RNA by binding to it.

6-4- Biomedical applications (Anti-bacterial activity and Anti-fungal activity)

These polymer metal complexes have been screened against several microorganisms

for their antimicrobial and antifungal activity; the results revealed that the polymer

metal complexes show superior anti-microbial activity than polymeric resin . It was

reported synthesis, characterization, and antimicrobial activities of phenylurea

formaldehyde resin (PUF) and its polymer metal complexes [PUF–M(II)]. The

antimicrobial activity of these resin were tested against six bacteria (Bacillus

subtelillis, Bacillus megaterium, Staphylococcu aureus, Escherichia coli,

Pseudomonas aeruginosa, Salmonella typhi) and six fungi (Candida albicans,

Tubercularia species, Aspergillus flavus, Aspergillus niger, Fusarium species, Mucer

species). Their findings was that the antimicrobial activity of the PUF–Cu(II) showed

the highest zone of inhibition because of its higher stability constant and may be used

in biomedical applications. (Ahamad & Alshehri. 2012)[40]


6-4-1Antimicrobial activity

Patel et al 2009 reported synthesize polymer-metal complexes of phenolic resin and

the its Antimicrobial activity of polymermetal complexes against Escherichia coli,

Bacillus subtilis, Staphylococcus aureus (bacteria) and Saccharomyces cerevisiae

(yeast) were measured. It is observed that polymer-metal complexes are efficient and

effective catalysts and antimicrobial agents.[41]

6-5- Polymeric Ligands in Metal Ion Separations

An important application of polymer supported ligands is in the selective separation

of metal ions and efforts in the recovery of metal ions from aqueous solutions using

polymeric chelating agents are steadily increasing. lo2-lo6. separation of metal ions is

realised only by using polymeric ligands and by making use of the dependencies of

the stability of the metal complex upon the structure of the ligands and the kind of

metal ions. Although it is possible to separate some definite metal ion from a mixture

of metal ions, it has not yet been possible to adsorb or complex any desired

metal ion selectively from a mixture of metal ions.

Removal, separation, and enrichment of hazardous metal ions in aqueous solutions

play an important role for environmental remediation of municipal and industrial

wastewater. Heterogeneous methods have been used for the separation of inorganic

ions contained in natural waters, industrial fluids, or dissolved solid materials.

The efficient and selective separation of inorganic ions can be achieved by using

water-soluble, polymeric reagents in combination with membrane filtration [42]. This

technique, developed in our laboratory, termed liquid-phase polymer-based retention

(LPR), is based on the separation of ions bound to water-soluble polymers with

chelating groups (polychelatogens) from noncomplexed ions [43,44,45]. It has found

application in the recovery of metals from diluted solutions both on an analytical and

technical scale.


6-6-Solar Energy

Dye-sensitized solar cells (DSSCs) have been proven to be a promising

alternative to conventional solar cells because of the low cost, abundant material

source, easy fabrication, and low energy consumption in the production processes

Jin et al 2013 reported that , It was successfully synthesized four D-π-A type main

chain polymericmetal complexes and used them as dye sensitizers in DSSCs. The

results show that the introduction of a strong electron donor thiophene and

phenanthroline derivative metal complexes to the molecular skeleton, which is

conducive to broaden the spectral absorption range of polymeric metal complexes.

In addition ,the study results show the four polymers exhibit good thermally stable

and the solar cells based on them have good device performance, and the

maximumpower conversion efficiency is up to 0.735% for the solar cells based on

P3with a short-circuit current (Jsc) of 1.68 mA/cm2 and an open-circuit voltage (Voc)

of 0.62V.[46]

6-7 Semi conductivity

The semiconducting properties of polymer metal complexes such as phthalocyanine,

polyferrocene. polyacetic acid metal complex, polyamino quinone

metal complex etc. have been well known and well studied.These are widely

employed in the research of semiconductors. ( Chacko - 2010 )[20]


Acknowledgements:

First of all I would like to thank Allah for his blessing and guidance without which I

could not finish this work. I would like also to thank the University of King Saud ,

School of Chemistry for Academic resources and facilities.


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Coordination polymer polymer metal complexes research chem620 finaly-awad albalwi

Science

polymermetal complexes2

polymermetal complex1

metal ionexample

metal ion2

metal atoms

polymermetal complex

metal ion separations6

polymeric metal complexes