Coordination Polymers of Polycarboxylates:Design, Synthesis and Structures

COORDINATION POLYMERS OF

POLYCARBOXYLATES:

DESIGN, SYNTHESIS AND

STRUCTURESPhD student | Scientific advisors

Ioana Georgeta Grosu| Prof. Dr. Evamarie Hey-Hawkins, Prof. Dr. Luminiţa Silaghi-

Dumitrescu

Faculty of Chemistry and Chemical

Engineering

“Babes-Bolyai” University

M. Kogălniceanu 1, 400082

Cluj-Napoca, Romania

Institute of Inorganic

Chemistry

Universität Leipzig

Johannisallee 29, 04103

Leipzig, Germany

[TABLE OF CONTENT]

1. Introduction

2. Generalities

3. Synthesis of the Ligands

4. Synthesis and Molecular Structure

of the Building Blocks

5. Coordination Polymers of 1,4-

phenylenebis(oxy)diacetic acid 1


phenylenebis(oxy)diacetic acid 2


phenylenebis(thio)diacetic acid 3

8. Coordination Polymers of N,N,N’N’-

1, 2-phenylene-diaminetetraacetic

acid 4

9. Coordination polymer starting from

complex 7 as building block

10. DTA Measurements

11. Experimental Part

12. General Conclusions

Appendix

[GENERALITIES] WHAT ARE COORDINATION POLYMERS?

Dimensionality of the coordination polymers

(M metal ions, D donor groups of the ligand, S spacer

within the ligand)

[GENERALITIES] SYNTHESIS OF COORDINATION POLYMERS

The building block principle for the synthesis of

coordination polymers

[GENERALITIES]ORGANIC LIGANDS IN THE SYNTHESIS OF COORDINATION

POLYMERS

Examples of ligands used for the synthesis of

coordination polymers

S. Kitawaga, S. Noro, Compreh. Coord. Chem., 2004, 7, 231

[SYNTHESIS OF THE LIGANDS] CHOSEN LIGANDS FOR THE SYNTHESIS OF COORDINATION

POLYMERS

[SYNTHESIS OF THE LIGANDS] SYNTHESIS OF 1,4-PHENYLENEDI(OXY)DIACETIC ACID 1

X. L. Hong, Y. Z. Li, Y. Pan, J. Bai and X. Z. You, Cryst. Growth Des., 2006, 6, 1221

[SYNTHESIS OF THE LIGANDS] SYNTHESIS AND MOLECULAR STRUCTURE OF 1,2-

PHENYLENEDI(THIO)DIACETIC ACID 3

Berghof, I. G. Grosu, P. Lönnecke, S. Gómez-Ruiz, L. Silaghi-Dumitrescu, E. Hey-Hawkins, Inorganica Chimica Acta – submitted

M. V. R. Reddy, S. Reddy and P. V. R. Reddy, Phosphorus, Sulfur and Silicon, 1989, 44, 1231

Packing diagram of 3, view

along b-axis

Molecular structure of 3

C2/c,

monoclinic

Z = 4

[SYNTHESIS OF THE LIGANDS] SYNTHESIS OF N,N,N’N’-1, 2-PHENYLENE-

DIAMINETETRAACETIC ACID 4

A. Mederos, J. V. Herrera, J. M. Felipe and M. Hernandez-Padilla, Anales de Quimica, 1985, 82, 150

[BUILDING BLOCKS] SYNTHESIS AND MOLECULAR STRUCTURE OF 5

Molecular structure of 5 THF-carboxylate hydrogen

bonding interactions in 5

[BUILDING BLOCKS] MOLECULAR STRUCTURE OF 5

P 1 ,

triclinic

Z = 2

Ag-Ocarboxylate: 2.498(1)Å

and 2.512(1)Å

Ag-OTHF: 2.338(2)Å

Ag···C: 2.533(2)Å

[BUILDING BLOCKS] COMPLEXES OF 3

C. Berghof, I. G. Grosu, P. Lönnecke, S. Gómez-Ruiz, L. Silaghi-Dumitrescu, E. Hey-Hawkins, Inorganica Chimica Acta – submitted

Christianne Berghof, Dissertation, Leipzig University, 2007

Two-dimensional hydrogen bonded

network of 8, a view along b-axisMolecular structure of 8

[BUILDING BLOCKS] MOLECULAR STRUCTURE OF 8

P 1 ,

triclinic

Z = 2

Ni-N: 2.035(1) Å and

2.037(1) Å

Ni-O: 2.043(9) Å

and 2.044(9) Å

Ni-S: 2.431(4) Å and

2.453(4) Å

Centrosymmetric dimers formed from

Δ and isomers

C. Berghof, I. G. Grosu, P. Lönnecke, S. Gómez-Ruiz, L. Silaghi-Dumitrescu, E. Hey-Hawkins, Inorganica Chimica Acta - submitted

[BUILDING BLOCKS] SYNTHESIS AND MOLECULAR STRUCTURE OF 10

C2/c ,

monoclinic

Z = 4

Pd-N:

2.092(2) Å

Pd-Cl:

2.219(6) Å

[COORDINATION POLYMERS

OF 1] SYNTHESIS

η1: η1: η1: η1: µ2

coordination mode of the

dianion of 1 in 12

η2: η1: η1: η1: µ3

coordination mode of the dianion of

1 in 13

[Cd{1,4 ̶(OOCCH2O)2C6H4}{C5H5N}3}]n

12

[Cd2{1,4 ̶(OOCCH2O)2C6H4}2{C10H8N2}{H2O}

2]n13


OF 1] MOLECULAR STRUCTURE OF 12

Coordination environment of the Cd2+ ions

in 12

Cd-N: 2.344(4) – 2.385(4)

Å

Cd-Ocarboxylate: 2.335(1) –

2.543(1) Å

P 1

, triclinic

Z = 2

Two-dimesional hydrogen bonded (dashed lines) network of

12



One dimensional chain of 12, a view along c-axis

P 1 ,

triclinic

Z = 2



Coordination environment of the Cd2+ ions in 13

P21/n ,

monoclinic

Z = 2

Cd-Ocarboxylate: 2.391(1) –

2.624(9) Å

Cd-Owater : 2.236(1)Å

Cd-N: 2.319(1) Å

Three-dimensional hydrogen bonded (dashed lines) network of 13



Dimetalla

macrocycle

Cd. . . Cd: 12.377(4) Å

Two-dimensional sheet of 13

Cd. . . Cd: 4.577(2) Å b-axis


OF 1] THERMAL PROPERTIES OF 13

TG curve coupled with mass ion current of water (green) and

carbon dioxide (violet) of 13

Decomposition

temperature: 260 o C


OF 2] SYNTHESIS

Two-dimensional hydrogen bonded (dashed

lines) network of 16


OF 2] SYNTHESIS

P 1 ,

triclinic

Z = 2

Cu-O: 2.086(1) Å and

2.151(1) Å

Cu-N: 1.925(1) Å and

1.929(1) Å

Ladder structure of 16, a view along a-axis

Coordination environment

of the Cu1+ ions in 16



TG curve of 16

Decomposition




Coordination environment of the

Ni2+ ions in 17

P21/ n

, monoclinic

Z = 4

Ni-Ocarboxylate: 2.064(8)

Å and 2.049(8) Å

Ni-Owater : 2.083(9)

Å and 2.058(9) Å

Ni-N: 2.109(9) Å and

2.105(9) Å



One-dimensional double chain formed by nickel ions and carboxylate oxygen atoms in 17, a view along a-axis

Ni. . .Ni:

5.206(2) Å



Two-dimensional sheet of 17

Ni. . .Ni: 11.292(2)

Å a-axis

Three-dimensional hydrogen bonded (dashed lines)

network of 17

Red polyhedra denote the NiO4N2 cluster



TG curve (green) and mass ion current curves of water

(red),

carbon monoxide (blue) and carbon dioxide (olive) of 17

Decomposition



OF 2] MOLECULAR STRUCTURES OF 18 AND 19

P2/n ,

monoclinic

Z = 2


metal ions in 18

(M1 = Zn) and 19 (M1 = Ni)

Ca-Oether : 2.448(7) –

2.493(1) Å

Ca-Ocarboxylate : 2.333(1) –

2.345(8) Å

Zn-Ocarboxylate : 2.134(1) Å

Zn-Owater : 2.061(9)

Å and 2.110(8) Å

Ni-Ocarboxylate : 2.073(1) Å

Ni-Owater : 2.043(1) Å

and 2.068(1) Å


OF 2] MOLECULAR STRUCTURES OF 18 AND 19

One-dimensional double chain of 18 and 19, a view along b-

axis

Three-dimensional hydrogen

bonded (dashed lines) network of

18, a view along b-axis


OF 3] SYNTHESIS



Molecular structure of 22

P1 , triclinic

Z = 1

Mn-N: 2.278(3) –

2.327(3) Å

Mn-Ocarboxylate : 2.202(3) Å

Mn-Owater : 2.150(3) –

2.199(3) Å



Intramolecular hydrogen bonding (dashed lines) in 22Three-dimensional hydrogen bonded (dashed lines) network of 22




Mn5+ ions in 23

Mn-N: 2.319(1) Å

Mn-Ocarboxylate : 2.101(9) –

2.205(8) Å

P21/ c

, monoclinic

Z = 2



Mn-O one-

dimensional chain

Mn. . . Mn:

3.50(1) Å

Mn. . . Mn:

4.44(1) Å Two-dimensional sheet of 23, a view

along a-axis



Three-dimensional network of

23,

a view along b-axis

Type 1

cavity

Type 2 cavity

Mn. . . Mn: 12.624(2) Å and 14.360(2)

Å c-axis

Mn. . . Mn: 13.282(2) Å a-axis



TG curve (green) and mass ion current curves of water

(red), carbon monoxide (blue) and carbon dioxide (olive) of

23

Decomposition



OF 4] SYNTHESIS



Coordination environment of the Cd2+

ions in 24

P21/n ,

monoclinic

Z = 4

Cd- N : 2.413(2) Å and

2.439(2) Å

Cd-Ocarboxylate : 2.264(1) Å -

2.600(3) Å

Cd-Owater : 2.274(4)

Å and 2.256 (5) Å



Three-dimensional layered structure of 24, a view

along a-axis

Cd. . . Cd: 8.578(2) Å

(b-axis)

Cd. . . Cd: 8.085(1) Å

(c-axis)



Decomposition


TG curve coupled with mass ion current of water (red),

carbon monoxide (olive) and carbon dioxide (blue) of 24



Coordination environment of the Ni2+ ions in 26

C2/c, monoclinic

Z = 4

Ni-Npyridyl : 2.071(1) - 2.112 (2) Å

Ni-Namino : 2. 077(1) Å and

2.071 (1) Å

Ni-Ocarboxylate : 2.029(1) – 2.600(3)

Å

Ni-Owater : 2.098(1) Å and

2.035 (1) Å



Ni(1). . . Ni(1):

13.068(5) Å

(a-axis)

Ni(1)···Ni(1):

15.097(5) Å

(b-axis)

Ni(2). . . Ni(2):

16.803 (9) Å

(a-axis)

Ni(1)···Ni(1):

11.512(4) Å

(b-axis)

Ni(1). . . Ni(2):

6.917(2) Å (b-

axis)

Three-dimensional network of 26, a view along c-

axis

Three-dimensional network of 26, a view along c-

axis.

Green polyhedra denote the NiO3N3 and NiO4N2

[COORDINATION POLYMER OF

7] SYNTHESIS


OF 7] COORDINATION MODES OF [(OOCCH2S)2C6H4]

2- IN 28

ω(S-Calkyl):169.16(1)o

and - 85.94(1)o

ω(S-Calkyl):165.04(1)o

and - 68.38(1)o

ω(S-Calkyl):81.22(1)o and -

175.14(1)o

Type 3Type 2

Type 1



Coordination environments of the Cd2+ and Ag1+

ions in 28

P21, monoclinic

Z = 2

Cd-Ocarboxylate : 2.255(2) -

2.295(2) Å

Cd(1)-Owater : 2.247(2) -

2.344(2) Å

Ag-S: 2.527(7) -

2.604(8) Å

Ag- Ocarboxylate : 2.434(2) Å

and 2.482(2) Å



Two-dimensional structure of 28

Ag. . . Ag: 5.899(1) Å (a-axis)

9.110(1) Å (b-axis)

Cd. . . Cd: 3.735(0) Å and

5.537(1) Å (a-axis)

10.955(1) Å and

13.996(1) Å (b-axis)



Three-dimensional hydrogen bonded

(dashed lines) network of 28

Gray polyhedra denote the

CdO5 and CdO6 clusters,

violet polyhedra denote the

AgS3O cluster

[CONCLUSIONS]

• three new complexes: [Ag2{1,2-(HOOCCH2O)2C6H4)- ĸ2, O,

O’}2{THF}2](BF4)2(5), [Ni{1,2-(OOCCH2S)2C6H4-ĸ4O,O’S,S’}{cis-

(C3H4N2)}2] (8) and cis-[PdCl2{1,2-((MeOOC)2N)2C6H4-κ2 N, N’}](10) as

potential building blocks for the synthesis of coordination polymers were

synthesized and characterized.

• seven cadmium coordination polymers were synthesized of which: three

one dimensional coordination polymers: [Cd{1,4-

(OOCCH2O)2C6H4}{C6H5N}2{H2O}]n (11), [Cd{1,4-

(OOCCH2O)2C6H4}{C5H5N}3}]n (12) and [Cd{1,2-(OOCC

OOCCH2O)2C6H4}{ H2O}2]n.(H2O)n; two two dimensional mixed ligand

polymers: [Cd2{1,4-(OOCCH2O)2C6H4}2{C10H8N2}{H2O}2]n (13) and

[Cd2{1,2-(OOCCH2O)2C6H4}2{C10H8N2}{H2O}2.7H2O]n (15) and two three

dimensional coordination polymers: [Cd2{1,2-

((OOCCH2)2N)2C6H4}{H2O}2]n (24) and the mixed ligand polymer [Cd4{1,2-

((OOCCH2)2N)2C6H4}{C10H8N2}2{H2O}2.4.25H2O]n (25)

• one copper one dimensional mixed ligands coordination polymer

[Cu2{1,2-(OOCCH2O)2C6H4}{ C10H8N2}2.2H2O]n (16) was synthesized, the

hydrothermal conditions and the presence in the reaction media of 4,4’-

bipyridine leading to the reduction of Cu(II) to Cu(I)

[CONCLUSION]

• three manganese new compounds have been synthesized: one mixed

ligand three dimensional polymer[Mn2{1,2-

(OOCCH2S)2C6H4}2{C10H8N2}]n(23), one two dimensional coordination

polymer [Mn2{1,2-((OOCCH2)2N)2C6H4}{H2O}4.H2O]n (27) and one

binuclear complex [Mn2{1,2-(OOCCH2S)2C6H4-κ1 S}{C10H8N2-κ

1 N}2 ,{

C10H8N2-κ2 N’, N’’}{H2O}7]

.[1,2-(OOCCH2S)2C6H4].[ C10H8N2]

.6H2O (22)

• three heterobimetallic coordination polymers have also been obtained:

one Ca/Zn one dimensional polymer [CaZn{1,2-

(OOCCH2O)2C6H4}2{H2O}4.4H2O]n (18) and one Ca/Ni one dimensional

polymer [CaNi{1,2-(OOCCH2O)2C6H4}2{H2O}4.4H2O]n (19), both of them

obtained in hydrothermal conditions but also one two dimensional Ag/Cd

coordination polymer [Ag2Cd2{1,2-(OOCCH2S)2C6H4}3{H2O}3.5H2O]n (28)

obtained at room temperature starting from the silver complex 7 as

building block.

• ligands 1-4 adopt different coordination modes depending on the metal to

which they coordinate and/or of the use of coligand. The dicarboxylate

ligands 1-3 adopt semi-flexible conformations while the tetracarboxylate

ligand 4 adopts a flexible conformation.

• the use of 4, 4’-bipyridine as coligand increases the dimensionality of the

[CONCLUSION]

• the synthesis of the manganese compounds: the binuclear complex 22,

the three dimensional coordination polymer 23 and the two dimensional

polymer 27 depends on the pH value of the reaction mixture (See 22 vs

23) or of the presence in the reaction media of 4, 4’-bipyridine (See 27).

• the intermolecular hydrogen bonding interactions: between solvate water

molecules and/or carboxylate oxygen atoms and coordinated water

molecules as well as between carboxylate oxygen atoms and coordinated

water molecules lead to the formation of hydrogen bonded

supramolecular networks of superior dimensionalities.

POLYCARBOXYLATES:

DESIGN, SYNTHESIS AND

STRUCTURES

PHD THESIS OF IOANA GROSU

Thank you for your

attention!

ACKNOWLEDGEMENTSThis work was generously financially supported

by:

• SOE

• Deutscher Akademischer Austauschdienst (DAAD)

• CEEX Romanian Research Grants

ACKNOWLEDGEMENTS

Thanks to:

• Prof. Dr. Evamarie Hey-Hawkins

• Prof. Dr. Luminita Silaghi-Dumitrescu

• Dr. Santiago Gómez Ruiz (X-ray diffraction)

• Dr. Peter Lönnecke (X-ray diffraction)

• Prof. Dr. B. Kersting (magnetic measurements)

• Mr. J. Lach (magnetic measurements)

• Frau Zäbe (NMR)

• Frau Scholz (IR)

• Johanna Zander (library)

ACKNOWLEDGEMENTS

Thanks to:• Prof. L. Silaghi-Dumitrescu’s group

• AK. E. Hey-Hawkins

Family and friends

My colleagues

I would like to invite you all to cantina

lounge

Documents

Coordination Polymers of Polycarboxylates:Design, Synthesis and Structures