DYNAMIC MULTICOMPONENT NANOSCALE AGGREGATES FLUORESCENCE, ECL AND COMPLEXATION OF C60
M. Schmittel, V. Kalsani, R. S. K. Kishore, B. He, P. Mal, L. Chen
Center of Micro- and Nanochemistry and Technology, Organische Chemie I, Univ. of Siegen, D-57068 Siegen, GERMANY
schmittel@chemie.uni-siegen.de
Universität Siegen
Fluorescent Nanoladders
Heteroleptic binding motifs used in our work:
Goal: The design of photoactive assemblies is a blossoming area of research in the field of supramolecular chemistry
since these architectures can act as sensoric materials for various purposes. Goal of this work is to develop a novel
and general supramolecular toolkit to engineer photoactive architectures, possessing large internal voids.
N
A concave metallophenanthroline receptor
Mn+
N
Ligands:
6
N
1'
R1
R
N
1
N N
Zn(II) N
N N
zz
8+
.8OTf
N
R
2
or
2
N
6
N
; n = 0; R1 =
1A = R =
or
= Zn2+
Br
N
N
1
; n = 1; R =
1B = R =
N
L1
1A
2
HETTAP approach
Heterotopic terpyridine and
phenanthroline complexes
HETPHEN approach
Heteroleptic bisphenanthroline
complexes
1''
N
R1
3
4
5
N
n
R
L2
1B
[L1.3OTf]5+
Characterization:
813.9
Expt.
H1’
H6’
813.7
813.5
H1’’
Mes
Mes
H7 H5&H6
814.1
814.3
814.5
813.3
814.9
815.1
815.3
815.5
813.1
H3’
H3
H4 H2’
812.9
H5’ H4’
Calcd.
814.7
CH2Cl2
815.7
812
L1: NMR:
N
9.6
9.2
8.8
8.4
7.6 7.2
(ppm)
8.0
N
N Zn
12+
.12OTf
4
3
N
R
N N
Cu+
N
N
Self-assembly:
5
7
N
N
N
N Zn
N
6.8
6.4
6.0
5.6
814
816
818
5.2
L1: ESI MS
N
N
HyperChem model of L2
L1
1A
1000
1B
~6 nm
L2
3-Component HETPHEN Nanostructures
~2.6 nm
I (a.u.)
800
Emission
In DCM/methanol (8:2)
600
400
200
~ 3.5 nm
0
300
400
500
600
700
wavelength (nm)
~ 1. 2 nm
= Cu(I) or Ag (I)
N
N
N
N
N
Br
N
Zn
Cu
N
N
N
N
Br
N
N
Cu
N
N
N
Cu
N
M. Schmittel, V. Kalsani, R. S. K. Kishore, H. Cölfen, J. W. Bats, J. Am. Chem. Soc. 2005, 127, 1154511546. Unpublished work by V. Kalsani and P. Mal.
Electrochemiluminescent Nanoladders
N
Cu
N
Br
N
N
Br
10
cl-Zn-ladder-2_060831165526#215 RT: 4.47 AV: 1 NL: 2.70E6
T: + c Full ms [ 150.00-2000.00]
953.0
100
95
Heteroleptic Triple
Nanodecker
Basket Structure (top) and
Porphyrin Aggregate
N
Zn
N
N
N
N
N
70
N
Br
Conclusion: A novel supramolecular toolkit is developed to generate
photoactive nanoscale ladder aggregates.
6+
2 Ir(pq)2(OTf) 2
65
Br
Ir
N
N
(OTf) 3
55
M. Schmittel, R. S. K. Kishore, Org. Lett. 2004, 6, 1923-1926; M. Schmittel, V. Kalsani, D. Fenske, A.
Wiegrefe, Chem. Comm. 2004, 490-491. V. Kalsani, H. Ammon, F. Jäckel, J. P. Rabe, M. Schmittel, Chem.
Eur. J. 2004, 10, 5481-5492. M. Schmittel, V. Kalsani, J. W. Bats, Inorg. Chem. 2005, 44, 4115-4117; M.
Schmittel, V. Kalsani, C. Michel, P. Mal, H. Ammon, J. P. Rabe, F. Jäckel, Chem. Eur. J. 2007, in press.
N
Ir(pq)2
45
N
L2
6+
Ir(pq)2
5+
(OTf) 5
828.2
1173.0
8+
599.7
703.8
689.4
(OTf)4
L2
935.6
572.1
286.9 364.5
1291.4
963.7
1504.5
948.3
10
5
4+
1173.8
573.4
(OTf)2
15
N
(OTf)3
776.0
7+
Ir(pq)2(OTf) 2
25
Zn
N
N
N
+
40
20
N
N
Zn
N
795.9
601.7
50
30
Br
Zn-ladder
N
954.1
7+
60
35
Br
MS
80
75
N
N
6+
85
Zn
N
(OTf) 4
90
N
N
Relative Abundance
Heteroleptic 3x3 Nanogrids
969.5
1140.6
1176.3
1502.2
1357.2
490.9
1505.4
1655.1
1652.9
1664.7 1782.8
0
N
N
200
400
600
800
1000
1200
1400
1600
1800
m/z
Ir
N
N
3500
L2
Zn ladder
3000
3-Component HETTAP Nanostructures
Intensity
2500
2000
ECL
1500
NMR
1000
300
400
500
600
700
800
900
Wavelength (nm)
Unpublished work by L. Chen
A C60 Guest in an Adaptive Supramolecular Prism
Heterotopic Nanoladder
Heterotopic Triple
Nanoladder
Supramolecular Prism
Dynamic 4-Component Nanostructures
N N
Cu
N
N
N
N
Zn N
N
Br
N
Tris -Phen(br)-Cu-Bis -Terpy(Por)+Fu-1#579-628 RT: 10.02-11.37 AV: 50 NL: 3.31E7
T: + c Full ms [ 150.00-2000.00]
N
Br
N
N
N
Zn N
N
C12H25
O
O
1352.8
100
95
C12H25
90
85
80
[M+C60-6PF6-]6+
75
70
N
N
N
C12H25
O
N
N
Zn N
N
N
Br
N N
Cu
N
MS
663.1
65
Relative Abundance
Cu
N N
60
55
50
- 5+
[M+C60-5PF6 ]
45
1652.0
40
1654.1
35
30
25
20
1354.5
15
1160.0
10
940.3
5
OC12H25
Br
N
Cu
NN
N
N
N
N Zn N
N
0
198.2 322.2 395.7 462.3
200
400
654.2
648.6
600
711.5
713.5 806.8
800
1362.7
1065.4
942.9
1000
1351.7
1245.4
1200
1630.6
1629.7
1511.8
1400
1663.5
1683.5
1600
1825.0 1901.0
1800
2000
m/z
Unpublished work by Bice He and P. Mal.
N
PT·3c (1:1.5)
Supramolecular PET Tetrade
‚Porphyrin Stack‘
R. S. K. Kishore, T. Paululat, M. Schmittel, Chem. Eur. J. 2006, 12, 8136-8149. M. Schmittel, R. S. K.
Kishore, J. W. Bats, Org. Biomol. Chem. 2007, 5, 78 - 86.
Conclusions: A large variety of dynamic nanostructures with interesting fluorescence, electrochemiluminescence and host/guest properties can be fabricated using the HETPHEN and HETTAP protocols.
Acknowledgments:
We are greatly indebted to the Deutsche Forschungsgemeinschaft for financial support and to the Fonds der
Chemischen Industrie for continued assistance. We are also thankful to Dr. J W Bats for the single crystal measurments
and Prof. Luisa De Cola for photophysical investigations.