Photoluminescent supramolecular networks from metal-mediated assembly of polythia conjugated dieneyne

Article abstract of DOI:10.1039/b212789j

Polythia conjugated dieneyne 1,1,2,5,6,6-hexakis(phenylthio)-1,5-diene-3-yne and its one- and two-dimensional silver(I) coordination polymers, which exhibited fluorescence and redox properties, were prepared and investigated.

Full text of DOI:10.1039/b212789j

Photoluminescent supramolecular networks from metal-mediated
assembly of polythia conjugated dieneyne
Yuan-Te Fu, Vincent M. Lynch and Richard J. Lagow*
Department of Chemistry and Biochemistry, The University of Texas at Austin, Austin, Texas 78712, USA.
E-mail: rjlagow@mail.utexas.edu
Received (in Columbia, MO, USA) 2nd January 2003, Accepted 13th March 2003
First published as an Advance Article on the web 31st March 2003
Polythia conjugated dieneyne 1,1,2,5,6,6-hexakis(phenyl-
thio)-1,5-diene-3-yne and its one- and two-dimensional
wave potential of +1.00 V vs. Ag wire was observed, which is
indicative of the formation of p-delocalized radical cations of
1.9
silver( ) coordination polymers, which exhibited fluores-
I
cence and redox properties, were prepared and investi-
gated.
The cyclic voltammogram of 2 in CH3NO2 containing 0.1 M
[(n-Bu)4N]PF6 is shown in Fig. 3b. Upon scanning in the
positive direction, two oxidation waves were observed; one
irreversible wave with a peak potential of 0.30 V vs. Ag wire
and another reversible wave with a half-wave potential of 0.41
V vs. Ag wire. These oxidation potentials of polymeric complex
2 are lower than those ones of ligand 1.
Luminescent polymers have received much attention due to
their potential application in emissive devices.1 Metal-directed
assembly has been used to generate coordination polymers
based on complexation of transition metals and multifunctional
bridging ligands and is one of many useful strategies to design
extended frameworks of various topology and dimension-
ality.2,3 Ligands with p-conjugated backbones may affect the
properties of the resulting polymers by promoting the couplings
of metal atoms through delocalized p-electron systems.4 It has
been of interest to use photoactive ligands as building blocks to
generate supramolecular polymers.1,5 We are currently in-
vestigating sulfur-containing unsaturated compounds with con-
jugated p-systems due to their useful electrochemical proper-
ties.6,7 Herein we report the syntheses, structures and electronic
properties of a new class of polythia conjugated dieneyne and its
silver( ) supramolecular networks.†
I
The synthesis of 1 was achieved by sequent treatment of
1,6-bis(p-toluenesulfonyloxy)-2,4-hexadiyne8 in THF at 278
°C with 4 equiv. of n-BuLi followed by an excess of Ph2S2
(Scheme 1). The emission spectrum of 1 is shown in Fig. 1. A
strong fluorescence band with lF,max = 492 nm was seen.
The reaction of 1 with AgCF3SO3 in THF and 1 with AgNO3
in THF/H2O at rt yielded polymeric coordination complexes 2
and 3, respectively. A red-shifted fluorescence band (lF,max
=
519 nm) relative to that of 1 was observed for polymer 2 (Fig.
2a). In contrast, compound 3 exhibited a slightly blue-shifted
emission band at lF,max = 481 nm (Fig. 2b).
Fig. 2 Solid-state emission spectrum (lex = 400 nm) of (a) 2 and (b) 3.
The cyclic voltammogram of 1 in CH2Cl2 containing 0.1M
[(n-Bu)4N]PF6 is shown in Figure 3a. Upon scanning the
potential positive, one quasi-reversible oxidation wave at half-
Scheme 1
Fig. 3 Cyclic voltammogram of 0.5 mM (a) 1 in CH2Cl2 containing 0.1 M
[(n-Bu)4N]PF6 (b) 2 in CH3NO2 containing 0.1 M [(n-Bu)4N]PF6.
Fig. 1 Solid-state emission spectrum of 1 (lex = 400 nm).
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CHEM. COMMUN., 2003, 1068–1069
This journal is © The Royal Society of Chemistry 2003

The crystal structure of 2 forms a two-dimensional coordina-
tion network with layers arranged perpendicular to c. Each layer
is composed of alternating regions of 1 and AgCF3SO3 (Fig.
4a).
are composed of Ag ions bridged by nitrate ions. As found in 2,
molecules of 1 also lie on crystallographic inversion centers.
The silver ion is four-coordinate with distorted tetrahedral
AgS2O2 coordination with Ag–O bond lengths of 2.397(2) and
2.404(2) Å and Ag–S bond lengths of 2.612(1) and 2.749(1) Å.
In contrast to the mode of coordination in 2, 1 binds to Ag in a
bidentate fashion (Fig. 5b) in 3. The architectures of two-
dimensional 2 and one-dimensional 3 indicate that the anions of
The asymmetric unit of 2 consists of two silver ions, two
bridging trifluorosulfonate ligands and half of the thioether
1
ligand 1, which lies on a crystallographic inversion center at ⁄2,
1
0, ⁄2. The coordination about the two Ag ions is different. Ag1
is four coordinate while Ag2 is five coordinate (Fig. 4b). The
coordination about Ag2 can be described as a distorted trigonal
bipyramid. The Ag–O bond lengths range from 2.442(5) to
2.742(6) Å. The Ag2–S bond length is 2.555(2) Å. The
tetravalent Ag1 ion has a coordination geometry approximating
a trigonal based pyramid. For Ag1, the Ag–O bond lengths
range from 2.317(6) to 2.515(5) Å with an Ag–S bond length of
2.452(2) Å. The coordination around Ag1 is essentially the
same as that around Ag2 with one of the axial O atoms
removed.
the silver(
I
) salts play an important role in the self-assembling
process.
In summary, a new type of photofunctional polythioalkene
with conjugated backbone has been synthesized and utilized as
a building block to generate photoactive one- and two-
dimensional supramolecular networks. These fluorescent com-
pounds may have potential application to optoelectronic
devices.
We thank the Welch Foundation for financial support of this
research.
The crystal structure of 3 was found to form a ladder-like one-
dimensional polymeric chain extended along a (Fig. 5a).
Molecules of 1 comprise the rungs of the ladder, while the sides
Notes and references
¯
†
Crystal data for 2: triclinic, space group P1 (no. 2), a = 10.4742(3), b
= 10.6734(3), c = 13.3298(4) Å, a = 77.106(2), b = 77.047(2), g =
88.948(2)°, V = 1414.88(7) Å3, Z = 2, Dc = 2.059 g cm23, µ(Mo–Ka) =
1.832 mm21, T = 153(2) K, l = 0.71073 Å, 9750 reflections collected,
6446 independent reflections (Rint = 0.0608), R1 = 0.0765, wR2 = 0.1643
[I > 2s(I)].
Crystal data for 3: C42H30Ag2N2O6S6, M = 1066.78, monoclinic, space
group P21/n, a = 5.6901(1), b = 16.3738(3), c = 21.0277(4) Å, b =
93.418(1)°, V = 1955.64(6) Å, Z = 2, Dc = 1.812 g cm23, m(Mo-Ka) =
1.375 mm21, T = 153(2) K, l = 0.71073 Å, 25019 reflections collected,
25019 reflections used in refinement, R1 = 0.0692, wR2 = 0.1358 [I >
2s(I)]. The data were corrected for twinning using ROTAX.10 The twin
fraction refined to 0.070(1). CCDC 200585 and 200586. See http://
www.rsc.org/suppdata/cc/b2/b212789j/ for crystallographic data in .cif or
other electronic format.
1 R. Dobrawa and F. Würthner, Chem. Commun., 2002, 1878; R. H.
Friend, R. W. Gymer, A. B. Holmes, J. H. Burroughes, R. N. Marks, C.
Taliani, D. D. C. Bradley, D. A. Dos Santos, J. L. Brédas, M. Lögdlund
and W. R. Salaneck, Nature, 1999, 397, 121; A. Kraft, A. C. Grimsdale
and A. B. Holmes, Angew. Chem., Int. Ed., 1998, 37, 402; J. R. Sheats,
H. Antoniadis, M. Hueschen, W. Leonard, J. Miller, R. Moon, D.
Roitman and A. Stocking, Science, 1996, 273, 884.
2 M.-C. Brandys and R. J. Puddephatt, J. Am. Chem. Soc., 2002, 124,
3946; G. D. Munno, M. Julve, F. Nicolo’, F. Lloret, J. Faus, R. Ruiz and
E. Sinn, Angew. Chem., Int. Ed., 1993, 32, 613; B. F. Abrahams, B. F.
Hoskins and R. Robson, J. Am. Chem. Soc., 1991, 113, 3606; E. Bosch
and C. L. Barnes, Inorg. Chem., 2002, 41, 2543.
3 M. Oh, G. B. Carpenter and D. A. Sweigart, Angew. Chem., Int. Ed.,
2001, 40, 3191; J. Kim, B. Chen, T. M. Reineke, H. Li, M. Eddaoudi, D.
B. Moler, M. O’Keeffe and O. M. Yaghi, J. Am. Chem. Soc., 2001, 123,
8239; S. Leininger, B. Olenyuk and P. J. Stang, Chem. Rev., 2000, 100,
853.
Fig. 4 (a) A drawing of a layer in 2 (b) a view of the coordination to Ag in
2 (fluorine atoms are omitted for clarity).
4 L. F. Szczepura, C. P. Galloway, Y. Zheng, P. Han, A. L. Rheingold, S.
R. Wilson and T. B. Rauchfuss, Angew. Chem. Int. Ed., 1995, 34,
1890.
5 L. Brunsveld, B. J. B. Folmer, E. W. Meijer and R. P. Sijbesma, Chem.
Rev., 2001, 101, 4071.
6 J. C. Zhong, Y. Misaki, M. Munakata, T. Kuroda-Sowa, M. Maekawa,
Y. Suenaga and H. Konaka, Inorg. Chem., 2001, 40, 7096; M. Adam and
K. Müllen, Adv. Mater., 1994, 6, 439.
7 T. Jørgensen, T. K. Hansen and J. Becher, Chem. Soc. Rev., 1994, 23,
41; M. R. Bryce, Chem. Soc. Rev., 1991, 20, 355.
8 Y. Rubin, S. S. Lin, C. B. Knobler, J. Anthony, A. M. Boldi and F.
Diederich, J. Am. Chem. Soc., 1991, 113, 6943.
9 P. C. B. Page, Top. Curr. Chem., 1999, 205, 1; H. Tani, Y. Kawada, N.
Azuma and N. Ono, Tetrahedron Lett., 1994, 35, 7051; T. Nabeshima,
S. Iwata, N. Furukawa, K. Morihashi and O. Kikuchi, Chem. Lett., 1988,
1325; T. Sugimoto, I. Sugimoto, A. Kawashima, Y. Yamamoto, Y.
Misaki and Z.-i. Yoshida, Heterocycles, 1987, 25, 83; D. L. Coffen, J.
Q. Chambers, D. R. Williams, P. E. Garrett and N. D. Canfield, J. Am.
Chem. Soc., 1971, 93, 2258.
Fig. 5 (a) View of 3 down the b-axis showing the ladder-like structure (b)
A view of the coordination to Ag in 3.
10 R. I. Cooper, R. O. Gould, S. Parsons and D. J. Watkin, J. Appl. Cryst.,
2002, 35, 168.
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