A pair of covalently linked molecular dyads is described in which two disparate boron dipyrromethene dyes are separated by a tolane-like spacer. Efficient electronic energy transfer (EET) occurs across the dyad; the mechanism involves important contributions from both Förster-type coulombic interactions and Dexter-type electron exchange processes. The energy acceptor is equipped with long paraffinic chains that favor aggregation at high concentration or at low temperature. The aggregate displays red-shifted absorption and emission spectral profiles, relative to the monomer, such that EET is less efficient because of a weaker overlap integral. The donor unit is insensitive to applied pressure but this is not so for the acceptor, which has extended π-conjugation associated with appended styryl groups. Here, pressure reduces the effective π-conjugation length, leading to a new absorption band at higher energy. With increasing pressure, the overall EET probability falls but this effect is nonlinear and at modest pressure there is only a small recovery of donor fluorescence. This situation likely arises from compensatory phenomena such as restricted rotation and decreased dipole screening by the solvent. However, the probability of EET falls dramatically over the regime where the π-conjugation length is reduced owing to the presumed conformational exchange. It appears that the pressure-induced conformer is a poor energy acceptor.
Conference
IUPAC Symposium on Photochemistry, International Symposium on Photochemistry, PHOTO, Photochemistry, XXIVth, Coimbra, Portugal, 2012-07-15–2012-07-20
References
1 10.1016/S0006-3495(03)75126-1, C. Berney, G. Danuser. Biophys. J.84, 3992 (2003).Search in Google Scholar
2 10.1016/j.tibs.2007.08.003, D. W. Piston, G.-J. Kremers. Trends Biochem. Sci.32, 407 (2007).Search in Google Scholar
3 10.1021/ja037088b, A. R. Clapp, I. L. Medintz, J. M. Mauro, B. R. Fisher, M. G. Bawendi, H. Mattoussi. J. Am. Chem. Soc.126, 301 (2004).Search in Google Scholar
4 10.1073/pnas.0408164102, B. Schuler, E. A. Lipman, P. J. Steinbach, M. Kumke, W. A. Eaton. Proc. Natl. Acad. Sci. USA102, 2754 (2005).Search in Google Scholar
5 10.1073/pnas.0508584102, T. A. Laurence, X. X. Kong, M. Jagger, S. Weiss. Proc. Natl. Acad. Sci. USA102, 17348 (2005).Search in Google Scholar
6 10.1016/j.bpj.2009.12.4322, H. S. Chung, J. M. Louis, W. A. Eaton. Biophys. J.98, 696 (2010).Search in Google Scholar
7 10.1073/pnas.96.17.9597, O. Bieri, J. Wirz, B. Hellrung, M. Schutkowski, M. Drewello, T. Kiefhaber. Proc. Natl. Acad. Sci. USA96, 9597 (1999).Search in Google Scholar
8 10.1021/ma800548r, A. Turshatov, J. Adams, D. Johannsmann. Macromolecules41, 5365 (2008).Search in Google Scholar
9 10.1039/b200595f, G. Srinivas, B. Bagchi. PhysChemComm5, 59 (2002).Search in Google Scholar
10 10.1016/S0006-3495(89)82918-2, J. M. Beechem, E. Haas. Biophys. J.55, 1225 (1989).Search in Google Scholar
11 10.1016/j.ymeth.2006.10.004, A. De Cian, L. Guittat, M. Kaiser, B. Sacca, A. Amrane, A. Bourdoncle, P. Alberti, M. P. Teulade-Fichou, L. Lacroix, J. L. Mergny. Methods42, 183 (2007).Search in Google Scholar PubMed
12 10.1038/nmat1508, C. Y. Zhang, H. C. Yeh, M. T. Kuroki, T. H. Wang. Nat. Mater.4, 826 (2005).Search in Google Scholar PubMed
13 10.1039/b817158k, M. K. R. Fischer, T. E. Kaiser, F. Wurther, P. Bauerle. J. Mater. Chem.19, 1129 (2009).Search in Google Scholar
14 10.1007/BF00585226, T. Förster. Naturwissenschaften6, 166 (1946).Search in Google Scholar
15 10.1063/1.1699044, D. L. Dexter. J. Chem. Phys.21, 836 (1953).Search in Google Scholar
16 10.1021/jp2068792, T. Kawatsu, K. Matsuda, J.-Y. Hasegawa. J. Phys. Chem. A115, 10814 (2011).Search in Google Scholar PubMed
17 10.1021/jp9917143, J. Ray, N. Makri. J. Phys. Chem. A103, 9417 (1999).Search in Google Scholar
18 10.1021/jp7106507, C. Curutchet, B. Mennucci, G. D. Scholes, D. Beljonne. J. Phys. Chem. B112, 3759 (2008).Search in Google Scholar PubMed
19 10.1021/ja044097r, A. C. Benniston, A. Harriman, P. Y. Li, C. A. Sams. J. Am. Chem. Soc.127, 2553 (2005).Search in Google Scholar PubMed
20 10.1021/jp961744v, S. Jockusch, H.-J. Timpe, W. Schnabel, N. J. Turro. J. Phys. Chem. A101, 440 (1997).Search in Google Scholar
21 10.1016/0022-2852(61)90233-8, G. W. Robinson. J. Mol. Spectrosc.6, 58 (1961).Search in Google Scholar
22 10.1021/ja300866s, T. A. Grusenmeyer, J. Chen, Y. Jin, J. Nguyen, J. R. Rack, R. H. Schmehl. J. Am. Chem. Soc.134, 7497 (2012).Search in Google Scholar PubMed
23 10.1039/b108200k, J. Andreasson, A. Kyrychenko, J. Martensson, B. Albinsson. Photochem. Photobiol. Sci.1, 111 (2002).Search in Google Scholar PubMed
24 10.1126/science.289.5483.1327, J. Yu, D. Hu, P. F. Barbara. Science289, 1327 (2000).Search in Google Scholar PubMed
25 10.1016/j.jphotochem.2005.02.006, S. Chatterjee, S. Nandi, S. C. Bhattacharya. J. Photochem. Photobiol., A173, 221 (2005).Search in Google Scholar
26 10.1021/ja00102a004, A. M. Brun, A. Harriman. J. Am. Chem. Soc.116, 10383 (1994).Search in Google Scholar
27 10.1021/jp903789y, J. Fiedor, M. Pilch, L. Fiedor. J. Phys. Chem. B113, 12831 (2009).Search in Google Scholar PubMed
28 B. Schuler. Methods Mol. Biol.115, 350 (2007).Search in Google Scholar
29 10.1073/pnas.0607097104, K. A. Merchant, R. B. Best, J. M. Louis, I. V. Gopich, W. A. Eaton. Proc. Natl. Acad. Sci. USA104, 1528 (2007).Search in Google Scholar PubMed PubMed Central
30 10.1039/c2sc00948j, M. A. H. Alamiry, J. P. Hagon, A. Harriman, T. Bura, R. Ziessel. Chem. Sci.3, 1041 (2012).Search in Google Scholar
31 10.1063/1.460740, M. Kato, Y. Taniguchi. J. Chem. Phys.94, 4440 (1991).Search in Google Scholar
32 10.1021/jp068287v, R. Sabharwal, Y. Huang, Y. Song. J. Phys. Chem. B111, 7267 (2007).Search in Google Scholar
33 S. T. Adamy, S. T. Kerrick, J. Jonas. Z. Phys. Chem. Int. J. Res. Phys. Chem. Chem. Phys.184, 185 (1994).10.1524/zpch.1994.184.Part_1_2.185Search in Google Scholar
34 10.1016/S0022-2836(03)00657-0, H. Herberhold, S. Marchal, R. Lange, C. H. Scheyhing, R. F. Vogel, R. Winter. J. Mol. Biol.330, 1153 (2003).Search in Google Scholar
35 10.1016/0032-3861(96)00425-9, S. Webster, D. N. Batchelder. Polymer37, 4961 (1996).Search in Google Scholar
36 10.1016/0301-0104(93)85105-H, Z. A. Dreger, J. M. Lang, H. G. Drickamer. Chem. Phys.169, 351 (1993).Search in Google Scholar
37 10.1021/jp900643m, A. Harriman, K. J. Elliot, M. A. H. Alamiry, L. Le Pleux, M. Severac, Y. Pellegrin, E. Blart, C. Fosse, C. Cannizzo, C. R. Mayer, F. Odobel. J. Phys. Chem. C113, 5834 (2009).Search in Google Scholar
38 10.1021/jp2070419, M. A. H. Alamiry, A. C. Benniston, G. Copley, A. Harriman, D. Howgego. J. Phys. Chem. A115, 12111 (2011).Search in Google Scholar PubMed
39 10.1021/j100102a008, S. Murphy, B. Sauerwein, H. G. Drickamer, G. B. Schuster. J. Phys. Chem.98, 13476 (1994).Search in Google Scholar
40 10.1021/jp022307l, A. Zhu, B. Wang, J. O. White, H. G. Drickamer. J. Phys. Chem. A107, 6932 (2003).Search in Google Scholar
41 10.1021/j100175a016, J. E. I. Korppi-Tommola, A. Hakkarainen, T. Hukka, J. Subbi. J. Phys. Chem.95, 8482 (1991).Search in Google Scholar
42 10.1080/0895795032000102379, K. Hara. High Press. Res.23, 225 (2003).Search in Google Scholar
43 10.1021/jp906009j, M. E. Madjet, F. Muh, T. Renger. J. Phys. Chem. B113, 12603 (2009).Search in Google Scholar
44 10.1039/c2ra00848c, M. A. H. Alamiry, A. C. Benniston, G. Copley, A. Harriman. RSC Adv.2, 1936 (2012).Search in Google Scholar
45 10.1562/0031-8655(2002)075<0327:FQYATR>2.0.CO;2, D. Magde, R. Wong, P. G. Seybold. Photochem. Photobiol.75, 327 (2002).Search in Google Scholar
46 10.1146/annurev.physchem.48.1.213, G. U. Bublitz, S. G. Boxer. Ann. Rev. Phys. Chem.48, 213 (1997).Search in Google Scholar
47 10.1021/bi00377a001, D. J. Lockhart, S. G. Boxer. Biochemistry26, 664 (1987).Search in Google Scholar
48 10.1021/ja00022a045, D. R. Crane, P. C. Ford. J. Am. Chem. Soc.113, 8510 (1991).Search in Google Scholar
49 10.1021/ja3007935, J.-H. Olivier, J. Barbera, E. Bahaidarah, A. Harriman, R. Ziessel. J. Am. Chem. Soc.134, 6100 (2012).Search in Google Scholar
50 10.1002/chem.201101407, J.-H. Olivier, J. Widmaier, R. Ziessel. Chem.—Eur. J.17, 11709 (2011).Search in Google Scholar
51 10.1002/chem.201001142, R. Ziessel, S. Rihn, A. Harriman. Chem.—Eur. J.16, 11942 (2010).Search in Google Scholar
52 10.1039/c0cc02687e, R. Ziessel, A. Harriman. Chem. Commun.47, 611 (2011).Search in Google Scholar
53 10.1021/jp026338s, S. Georgakopoulou, R. J. Cogdell, R. van Grondelle, H. van Amerongen. J. Phys. Chem. B107, 655 (2003).Search in Google Scholar
54 10.1021/jp003571m, G. D. Scholes, X. J. Jordanides, G. R. Fleming. J. Phys. Chem. B105, 1640 (2001).Search in Google Scholar
55 10.1021/jp037724s, K. F. Wong, B. Bagchi, P. J. Rossky. J. Phys. Chem.108, 5752 (2004).Search in Google Scholar
56 10.1103/PhysRevA.81.033825, D. L. Andrews. Phys. Rev. A81, 033825 (2010).Search in Google Scholar
57 10.1016/0009-2614(70)80220-2, V. Czikklely, H. D. Forsterling, H. Kuhn. Chem. Phys. Lett.6, 207 (1970).Search in Google Scholar
58 10.1021/ja9038856, A. Harriman, L. J. Mallon, K. J. Elliot, A. Haefele, G. Ulrich, R. Ziessel. J. Am. Chem. Soc.131, 13375 (2009).Search in Google Scholar PubMed
59 10.1021/ja00363a001, A. R. McIntosh, A. Siemiarczuk, J. R. Bolton, M. J. Stillman, T. F. Ho, A. C. Weedon. J. Am. Chem. Soc.105, 7215 (1983).Search in Google Scholar
60 10.1063/1.1492280, Q. H. Xu, M. D. Fayer. J. Chem. Phys.117, 2732 (2002).Search in Google Scholar
61 10.1063/1.1733166, S. J. Strickler, R. A. Berg. J. Chem. Phys.27, 814 (1962).Search in Google Scholar
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