[en] Piggy-back porphyrins: The presence of a Lewis base remarkably affects the cooperative self-assembly of zinc porphyrins. Driven by the susceptibility of the monomer towards the axial ligand, monomer scavenging caused depolymerization of porphyrin aggregates, and dilution caused aggregation by a re-entrant phase transition. Model predictions were validated by dilution experiments.
Disciplines :
Chemistry Physics
Author, co-author :
Helmich, F.
Lee, C.C.
Nieuwenhuizen, M.M.L.
Gielen, J.C.
Christianen, P.C.M.
Larsen, A.
Fytas, G.
Leclère, Philippe ; Université de Mons > Faculté des Sciences > Chimie des matériaux nouveaux
Schenning, A.P.H.J.
Meijer, A.W.
Language :
English
Title :
Dilution-Induced Self-Assembly of Porphyrin Aggregates: A Consequence of Coupled Equilibria
Publication date :
25 May 2010
Journal title :
Angewandte Chemie International Edition
ISSN :
1433-7851
Publisher :
Wiley, Weinheim, Germany
Volume :
49
Issue :
23
Pages :
3939-3942
Peer reviewed :
Peer Reviewed verified by ORBi
Research unit :
S817 - Chimie des matériaux nouveaux
Research institute :
R400 - Institut de Recherche en Science et Ingénierie des Matériaux
J. M. Lehn, Supramolecular Chemistry: Concepts and Perspectives, Wiley-VCH, Weinheim, 1995.
T. F. A. De Greef, M.M.J. Smulders, M. Wolffs, A. P. H. J. Schenning, R. P. Sijbesma, E. W. Meijer, Chem. Rev. 2009, 109, 5687.
P. G. A. Janssen, S. Jabbari-Farouji, M. Surin, X. Vila, J. C. Gielen, T. F. A. de Greef, M. R. J. Vos, P. H. H. Bomans, N. Sommerdijk, P. C. M. Christianen, P. E. L. G. Leclère, R. Lazzaroni, P. van der Schoot, E. W Meijer, A. P. H. J. Schenning, J. Am Chem. Soc. 2009, 131, 1222.
a) D. Furutsu, A. Satake, Y Kobuke, Inorg. Chem. 2005, 44, 4460;
b) R. P. Sijbesma, F. H. Beijer, L. Brunsveld, B. J. B. Folmer, J. Hirschberg, R. F. M. Lange, J. K. L. Lowe, E. W. Meijer, Science 1997, 278, 1601.
a) D. H. Zhao, J. S. Moore, Org. Biomol. Chem. 2003, 1, 3471;
b) D. H. Zhao, J. S. Moore, J. Am. Chem. Soc. 2003, 125, 16294.
a) J. Z. Li, H. Xin, M. Li, Liq. Cryst. 2006, 33, 913;
b) S. W. Kang, Q. Li, B. D. Chapman, R. Pindak, J. O. Cross, L. F. Li, M. Nakata, S. Kumar, Chem. Mater. 2007, 19, 5657;
c) M. Shirakawa, S. Kawano, N. Fujita, K. Sada, S. Shinkai, J. Org. Chem. 2003, 68, 5037;
d) M. Shirakawa, N. Fujita, S. Shinkai, J. Am. Chem. Soc. 2005, 127, 4164;
e) T. Kishida, N. Fujita, K. Sada, S. Shinkai, Langmuir 2005, 21, 9432;
f) F. J. M. Hoeben, M. Wolffs, J. Zhang, S. De Feyter, P. E. L. G. Leclère, A. P. H. J. Schenning, E. W. Meijer, J. Am. Chem. Soc. 2007, 129, 9819.
See the Supporting Information.
N. C. Maiti, S. Mazumdar, N. Periasamy, J. Phys. Chem. B 1998, 102, 1528.
Prior to the 30 nm blue-shift, the monomer band slightly broadens, which is probably due to the formation of an intermediate state that is weakly CD-active in the monomer absorbance range.
In the cooling curve, φ represents the normalized fraction of aggregated species. A similar cooling curve is observed when monitoring the CD intensity, suggesting that the formation of helical aggregates coincides just after nucleation. Upon further cooling from Te, the aggregate band shows a slight blue-shift; causing a small difference in the elongation regime of the cooling curve probed either by CD or UV/Vis spectroscopy.
M. M. J. Smulders, A. P. H. J. Schenning, E. W. Meijer, J. Am. Chem. Soc. 2008, 130, 606.
I. O. Shklyarevskiy, P. Jonkheijm, N. Stutzmann, D. Wasserberg, H. J. Wondergem, P. C. M. Christianen, A. P. H. J. Schenning, D. M. de Leeuw, Z. Tomovic, J. S. Wu, K. Müllen, J. C. Maan, J. Am. Chem. Soc. 2005, 127, 16233.
The association constant and spectral changes of 1 with pyridine were determined in chloroform, and showed a red-shift of the Soret band from 422 to 432 nm (KCHCl3 = 1.2x 104Lmol-1). In MCH, the addition of pyridine to an N-methylated analogue 1,[7] which is molecularly dissolved in this solvent, shows a red-shift from 419 to 429 nm and a five-fold higher association constant (Kc = 5.1x10 4 Lmol-1).[7]
V. V. Borovkov, J. M. Lintuluoto, Y. Inoue, J. Phys. Chem. B 1999, 103, 5151.
Possible two-fold coordination of pyridine to the Zn2+-ions is not expected to be significant in the concentration range of the titration and is not included in the model, which also does not describe the dissociation of pyridine-complexed dimers owing to polarity.
At a concentration of 1.2 x 10-5 mol L-1, 85 % of the binding sites is provided by monomers.[7]
C. A. Hunter, P. Leighton, J. K. M. Sanders, J. Chem. Soc. Perkin Trans. 1 1989, 547.
The parameters for the concentration-dependent K2K model are adapted from the parameters obtained from the temperaturedependent model: M. M. J. Smulders, M. M. L. Nieuwenhuizen, T. F. A. de Greef P. van der Schoot, A. P. H. J. Schenning, E. W. Meijer, Chem. Eur. J. 2010, 16, 362.[7]
a) J. M. Berg, J. L. Tymoczko, L. Stryer, Biochemistry, W. H. Freeman, San Francisco, 2002;
b) T. M. Hermans, M. A. C. Broeren, N. Gomopoulos, P. van der Schoot, M. H. P. van Genderen, N. Sommerdijk, G. Fytas, E. W. Meijer, Nat. Nanotechnol. 2009, 4, 721.
R. F. Ludlow, S. Otto, Chem. Soc Rev. 2008, 37, 101.
