Abstract
Two novel azoalkane bichromophores and related model compounds have been synthesised and photophysically characterised. Dimethylphenylsiloxy (DPSO) or dimethylnaphthylsiloxy (DNSO) serve as aromatic donor groups (antenna) and the azoalkane 2,3-diazabicyclo[2.2.2]oct-2-ene (DBO) as the acceptor. The UV spectral window of DBO (250–300 nm) allows selective excitation of the donor. Intramolecular singlet–singlet energy transfer to DBO is highly efficient and proceeds with quantum yields of 0.76 with DPSO and 0.99 with DNSO. The photophysical and spectral properties of the bichromophoric systems suggest that energy transfer occurs through diffusional approach of the donor and acceptor within a van der Waals contact at which the exchange mechanism is presumed to dominate. Furthermore, akin to the behaviour of electron-transfer systems in the Marcus inverted region, a rate of energy transfer 2.5 times slower was observed for the system with the more favourable energetics, i.e. singlet–singlet energy transfer from DPSO proceeded slower than from DNSO, although the process is more exergonic for DPSO (−142 kJ mol−1 for DPSO versus−67 kJ mol−1 for DNSO).
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W. M. Nau, X. Zhang, An exceedingly long-lived fluorescent state as a distinct structural and dynamic probe for supramolecular association: an exploratory study of host–guest complexation by cyclodextrins, J. Am. Chem. Soc., 1999, 121, 8022–8032.
C. Marquez, W. M. Nau, Polarizabilities inside molecular containers, Angew. Chem., Int. Ed., 2001, 40, 4387–4390.
W. M. Nau, A fluorescent probe for antioxidants, J. Am. Chem. Soc., 1998, 120, 12-614–12-618.
C. Marquez, U. Pischel, W. M. Nau, Selective fluorescence quenching of 2,3-diazabicyclo[2.2.2]oct-2-ene by nucleotides, Org. Lett., 2003, 5, 3911–3914.
G. Gramlich, J. Zhang, W. M. Nau, Increased antioxidant reactivity of vitamin C at low pH in model membranes, J. Am. Chem. Soc., 2002, 124, 11-252–11-253.
R. R. Hudgins, F. Huang, G. Gramlich, W. M. Nau, A fluorescence-based method for direct measurement of submicrosecond intramolecular contact formation in biopolymers: an exploratory study with polypeptides, J. Am. Chem. Soc., 2002, 124, 556–564.
W. M. Nau, X. Wang, Biomolecular and supramolecular kinetics in the submicrosecond time range: the fluorazophore approach, ChemPhysChem, 2002, 3, 393–398.
W. M. Nau, F. Huang, X. Wang, H. Bakirci, G. Gramlich, C. Marquez, Exploiting long-lived molecular fluorescence, Chimia, 2003, 57, 161–167.
F. Huang, W. M. Nau, A conformational flexibility scale for amino acids in peptides, Angew. Chem., Int. Ed., 2003, 42, 2269–2272.
W. M. Nau, G. Greiner, H. Rau, J. Wall, M. Olivucci, J. C. Scaiano, Fluorescence of 2,3-diazabicyclo[2.2.2]oct-2-ene revisited: solvent-induced quenching of the n,π*-excited state by an aborted hydrogen atom transfer, J. Phys. Chem. A, 1999, 103, 1579–1584.
W. M. Nau, G. Greiner, J. Wall, H. Rau, M. Olivucci, M. A. Robb, The mechanism for hydrogen abstraction by n,π* excited singlet states: evidence for thermal activation and deactivation through a conical intersection, Angew. Chem., Int. Ed., 1998, 37, 98–101.
A. Sinicropi, U. Pischel, R. Basosi, W. M. Nau, M. Olivucci, Conical intersections in charge-transfer induced quenching, Angew. Chem., Int. Ed., 2000, 39, 4582–4586.
H. E. Zimmerman, T. D. Goldman, T. K. Hirzel, S. P. Schmidt, Rod-like organic molecules. Energy-transfer studies using single-photon counting, J. Org. Chem., 1980, 45, 3933–3951.
H. Oevering, J. W. Verhoeven, M. N. Paddon-Row, E. Cotsaris, N. S. Hush, Long-range exchange contribution to singlet-singlet energy transfer in a series of rigid bichromophoric molecules, Chem. Phys. Lett., 1988, 143, 488–495.
J. Kroon, A. M. Oliver, M. N. Paddon-Row, J. W. Verhoeven, Observation of a remarkable dependence of the rate of singlet-singlet energy transfer on the configuration of the hydrocarbon bridge in bichromophoric systems, J. Am. Chem. Soc., 1990, 112, 4868–4873.
F. Schael, M. B. Rubin, S. Speiser, Electronic energy transfer in solution in naphthalene-anthracene, naphthalene-acridine and benzene-DANS bichromophoric compounds, J. Photochem. Photobiol., A, 1998, 115, 99–108.
S. Speiser, F. Schael, Molecular structure control of intramolecular electronic energy transfer, J. Mol. Liq., 2000, 86, 25–35.
G. L. Closs, M. D. Johnson, J. R. Miller, P. Piotrowiak, A connection between intramolecular long-range electron, hole, and triplet energy transfers, J. Am. Chem. Soc., 1989, 111, 3751–3753.
P. J. Wagner, P. Klán, Intramolecular triplet energy transfer in flexible molecules: electronic, dynamic, and structural aspects, J. Am. Chem. Soc., 1999, 121, 9626–9635.
N. J. Turro, Energy transfer processes, Pure Appl. Chem., 1977, 49, 405–429.
S. Speiser, Photophysics and mechanisms of intramolecular electronic energy transfer in bichromophoric molecular systems: solution and supersonic jet studies, Chem. Rev., 1996, 96, 1953–1976.
K. Razi Naqvi, C. Steel, Exchange-induced resonance energy transfer, Chem. Phys. Lett., 1970, 6, 29–32.
P. S. Engel, C. Steel, Photochemistry of aliphatic azo compounds in solution, Acc. Chem. Res., 1973, 6, 275–281.
P. S. Engel, L. D. Fogel, C. Steel, Singlet energy transfer to azoalkanes, J. Am. Chem. Soc., 1974, 96, 327–332.
C. C. Wamser, L. Lou, J. Mendoza, E. Olson, Singlet electronic energy transfer to azoalkanes: separation of collisional and long-range mechanisms by steric and solvent-viscosity effects, J. Am. Chem. Soc., 1981, 103, 7228–7232.
P. S. Engel, D. W. Horsey, J. N. Scholz, T. Karatsu, A. Kitamura, Intramolecular triplet energy transfer in ester-linked bichromophoric azoalkanes and naphthalenes, J. Phys. Chem., 1992, 96, 7524–7535.
Z.-Z. Wu, J. Nash, H. Morrison, Organic photochemistry. 97. Antenna-initiated photochemistry in polyfunctional steroids. Photoepimerization of 3α-(dimethylphenylsiloxy)-5α-androstane-6,17-dione and its 3β isomer by through-bond exchange energy transfer, J. Am. Chem. Soc., 1992, 114, 6640–6648.
Z.-Z. Wu, H. Morrison, Organic photochemistry. 95. Antenna-initiated photochemistry of distal groups in polyfunctional steroids. Intramolecular singlet and triplet energy transfer in 3α-(dimethylphenylsiloxy)-5α-androstan-17-one and 3α-(dimethylphenylsiloxy)-5α-androstane-11,17-dione, J. Am. Chem. Soc., 1992, 114, 4119–4128.
J. K. Agyin, L. D. Timberlake, H. Morrison, Steroids as photonic wires. Z→E olefin photoisomerization involving ketone singlet and triplet switches by through-bond energy transfer, J. Am. Chem. Soc., 1997, 119, 7945–7953.
T. R. van den Anker, C. L. Raston, Polymer- and metal-oxide-supported alkali metal naphthalenides: application in the generation of lithium and sodium reagents, J. Organomet. Chem., 1998, 550, 283–300.
W. M. Nau, n,π* Photochemistry beyond ketones, EPA Newsl., 2000, 70, 6–29.
K. A. Zachariasse, A. L. Maçanita, W. Kühnle, Chain length dependence of intramolecular excimer formation with 1,n-bis(1-pyrenylcarboxy)alkanes for n= 1–16, 22, and 32, J. Phys. Chem. B, 1999, 103, 9356–9365.
N. Lokan, M. N. Paddon-Row, T. A. Smith, M. La Rosa, K. P. Ghiggino, S. Speiser, Highly efficient through-bond-mediated electronic excitation energy transfer taking place over 12 Å, J. Am. Chem. Soc., 1999, 121, 2917–2918.
S. L. Murov, I. Carmichael and G. L. Hug, Handbook of Photochemistry, Marcel Dekker, Inc., New York, 2nd edn., 1993.
X. Wang, E. N. Bodunov, W. M. Nau, Fluorescence quenching kinetics in short polymer chains: dependence on chain length, Opt. Spectrosc., 2003, 95, 603–613.
To calculate the electron transfer energetics with the Rehm–Weller equation [ΔGet(kJ mol−1)= 96.5[Eox−Ered−E*+C]), and for the energy-transfer energetics [ΔGSSET=E*(Acceptor)−E*(Donor)], the following photophysical and electrochemical parameters (versus SCE in acetonitrile unless otherwise stated) were used: for DBO, E*= 3.30 eV (318 kJ mol−1), 10Eox= 1.45 V (cf. W. M. Nau, W. Adam, D. Klapstein, C. Sahin, H. Walter, Correlation of oxidation and ionization potentials for azoalkanes, J. Org. Chem., 1997, 62, 5128–5132) and Ered=−2.80 V (cf.
W. M. Nau, U. Pischel, “Inverted” solvent effect on charge transfer in the excited state, Angew. Chem., Int. Ed., 1999, 38, 2885–2888); for naphthalene, E*= 3.99 eV (385 kJ mol−1),34Eox= 1.60 V41 and Ered=−2.29 V41; for benzene E*= 4.75 eV (460 kJ mol−1),34Eox= 2.35 V (cf.
S. Fukuzumi, K. Ohkubo, T. Suenobu, K. Kato, M. Fujitsuka, O. Ito, Photoalkylation of 10-alkylacridinium ion via a charge-shift type of photoinduced electron transfer controlled by solvent polarity, J. Am. Chem. Soc., 2001, 123, 8459–8467) and Ered=−3.31 V versus SCE in 1,2-dimethoxyethane (cf.
F. Gerson, H. Ohya-Nishiguchi, C. Wydler, Indirect determination of the half-wave reduction potential of benzene and of [2.2]paracyclophane, Angew. Chem., Int. Ed. Engl., 1976, 15, 552–553). The Coulomb term (C) was taken as −0.06 eV.
G. L. Closs, P. Piotrowiak, J. M. MacInnis, G. R. Fleming, Determination of long distance intramolecular triplet energy transfer rates. A quantitative comparison with electron transfer, J. Am. Chem. Soc., 1988, 110, 2652–2653.
P. J. Wagner, R. J. Truman, A. E. Puchalski, R. Wake, Extent of charge transfer in the photoreduction of phenyl ketones by alkylbenzenes, J. Am. Chem. Soc., 1986, 108, 7727–7738.
C. Coenjarts, J. C. Scaiano, Reaction pathways involved in the quenching of the photoactivated aromatic ketones xanthone and 1-azaxanthone by polyalkylbenzenes, J. Am. Chem. Soc., 2000, 122, 3635–3641.
An interaction of both chromophores mediated by the spacer orbitals, i.e. a superexchange mechanism, was also considered. Its participation in the overall mechanism is presumably negligible, since considerable flexibility of the spacer chain reduces the probability of a favourable arrangement of σ orbitals.15,17 For triplet energy transfer in bichromophoric ω-aryloxyalkanophenones with flexible tethers, it was found that through-space energy transfer by the exchange mechanism is overwhelmingly predominant19.
G. J. Kavarnos, N. J. Turro, Photosensitization by reversible electron transfer: theories, experimental evidence, and examples, Chem. Rev., 1986, 86, 401–449.
M. Gisin, J. Wirz, Photolysis of the azo precursors of 2,3- and 1,8-naphthoquinodimethane, Helv. Chim. Acta, 1976, 59, 2273–2277.
S. J. Hagen, J. Hofrichter, W. A. Eaton, Rate of intrachain diffusion of unfolded cytochrome c, J. Phys. Chem. B, 1997, 101, 2352–2365.
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Pischel, U., Huang, F. & Nau, W.M. Intramolecular singlet–singlet energy transfer in antenna-substituted azoalkanes. Photochem Photobiol Sci 3, 305–310 (2004). https://doi.org/10.1039/b311416c
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DOI: https://doi.org/10.1039/b311416c