coordination polymers of polycarboxylates:design, synthesis and structures
Post on 14-Jul-2015
627 Views
Preview:
TRANSCRIPT
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
6. Coordination Polymers of 1,2-
phenylenebis(oxy)diacetic acid 2
7. Coordination Polymers of 1,2-
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
[COORDINATION POLYMERS
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
[COORDINATION POLYMERS
OF 1] MOLECULAR STRUCTURE OF 12
One dimensional chain of 12, a view along c-axis
P 1 ,
triclinic
Z = 2
[COORDINATION POLYMERS
OF 1] MOLECULAR STRUCTURE OF 13
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
[COORDINATION POLYMERS
OF 1] MOLECULAR STRUCTURE OF 13
Dimetalla
macrocycle
Cd. . . Cd: 12.377(4) Å
Two-dimensional sheet of 13
Cd. . . Cd: 4.577(2) Å b-axis
[COORDINATION POLYMERS
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
[COORDINATION POLYMERS
OF 2] SYNTHESIS
Two-dimensional hydrogen bonded (dashed
lines) network of 16
[COORDINATION POLYMERS
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
[COORDINATION POLYMERS
OF 2] THERMAL PROPERTIES OF 16
TG curve of 16
Decomposition
temperature: 260 o C
[COORDINATION POLYMERS
OF 2] MOLECULAR STRUCTURE OF 17
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
[COORDINATION POLYMERS
OF 2] MOLECULAR STRUCTURE OF 17
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
[COORDINATION POLYMERS
OF 2] MOLECULAR STRUCTURE OF 17
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
[COORDINATION POLYMERS
OF 2] THERMAL PROPERTIES OF 17
TG curve (green) and mass ion current curves of water
(red),
carbon monoxide (blue) and carbon dioxide (olive) of 17
Decomposition
temperature: 280 o C
[COORDINATION POLYMERS
OF 2] MOLECULAR STRUCTURES OF 18 AND 19
P2/n ,
monoclinic
Z = 2
Coordination environment of the
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
[COORDINATION POLYMERS
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
[COORDINATION POLYMERS
OF 3] SYNTHESIS
[COORDINATION POLYMERS
OF 3] MOLECULAR STRUCTURE OF 22
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
[COORDINATION POLYMERS
OF 3] MOLECULAR STRUCTURE OF 22
Intramolecular hydrogen bonding (dashed lines) in 22Three-dimensional hydrogen bonded (dashed lines) network of 22
[COORDINATION POLYMERS
OF 3] MOLECULAR STRUCTURE OF 23
Coordination environment of the
Mn5+ ions in 23
Mn-N: 2.319(1) Å
Mn-Ocarboxylate : 2.101(9) –
2.205(8) Å
P21/ c
, monoclinic
Z = 2
[COORDINATION POLYMERS
OF 3] MOLECULAR STRUCTURE OF 23
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
[COORDINATION POLYMERS
OF 3] MOLECULAR STRUCTURE OF 23
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
[COORDINATION POLYMERS
OF 1] THERMAL PROPERTIES OF 23
TG curve (green) and mass ion current curves of water
(red), carbon monoxide (blue) and carbon dioxide (olive) of
23
Decomposition
temperature: 280 o C
[COORDINATION POLYMERS
OF 4] SYNTHESIS
[COORDINATION POLYMERS
OF 4] MOLECULAR STRUCTURE OF 24
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
[COORDINATION POLYMERS
OF 4] MOLECULAR STRUCTURE OF 24
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)
[COORDINATION POLYMERS
OF 4] THERMAL PROPERTIES OF 24
Decomposition
temperature: 320 o C
TG curve coupled with mass ion current of water (red),
carbon monoxide (olive) and carbon dioxide (blue) of 24
[COORDINATION POLYMERS
OF 4] MOLECULAR STRUCTURE OF 26
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
[COORDINATION POLYMERS
OF 4] MOLECULAR STRUCTURE OF 26
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
[COORDINATION POLYMERS
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 POLYMERS
OF 7] MOLECULAR STRUCTURE OF 28
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
[COORDINATION POLYMERS
OF 7] MOLECULAR STRUCTURE OF 26
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)
[COORDINATION POLYMERS
OF 7] MOLECULAR STRUCTURE OF 28
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
top related