Photoinduced energy–electron transfer studies with naphthalene diimides

Alp, Serap; Erten, Sinan; Karapire, Canan; Köz, Banu; Дорошенко, А. О.; İçli, Sıddık

doi:10.1016/s1010-6030(00)00306-3

Cited by 66 publications

(33 citation statements)

References 11 publications

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“…Naphthalene diimide is a planar, conjugated molecule with a C 2v symmetry. The experimental S 0 –S 1 transition at 3.25 eV has been attributed to a π–π* excitation with a characteristic vibrational fine structure at 3.44 and 3.61 eV . The transition is considered to be insensitive to substituent effects with the bright colors of substituted derivatives attributed to a new intramolecular charge transfer band .…”

Section: Resultsmentioning

confidence: 99%

Substituent effects on the optical properties of naphthalenediimides: A frontier orbital analysis across the periodic table

Mulder

Guerra²,

Slootweg

et al. 2015

J Comput Chem

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A comprehensive theoretical treatment is presented for the electronic excitation spectra of ca. 50 different mono-, di-, and tetrasubstituted naphthalenediimides (NDI) using time-dependent density functional theory (TDDFT) at ZORA-CAM-B3LYP/TZ2P//ZORA-BP86/TZ2P with COSMO for simulating the effect of dichloromethane (DCM) solution. The substituents -XHn are from groups 14-17 and rows 2-5 of the periodic table. The lowest dipole-allowed singlet excitation (S0 -S1 ) of the monosubstituted NDIs can be tuned from 3.39 eV for -F to 2.42 eV for -TeH, while the S0 -S2 transition is less sensitive to substitution with energies ranging between 3.67 eV for -CH3 and 3.44 eV for -SbH2 . In the case of NDIs with group-15 and -16 substituents, the optical transitions strongly depend on the extent to which -XHn is planar or pyramidal as well as on the possible formation of intramolecular hydrogen bonds. The accumulative effect of double and quadruple substitution leads in general to increasing bathochromic shifts, but the increased steric hindrance in tetrasubstituted NDIs can lead to deformations that diminish the effectiveness of the substituents. Detailed analyses of the Kohn-Sham orbital electronic structure in monosubstituted NDIs reveal the mesomeric destabilization of the HOMO as the primary cause of the bathochromic shift of the S0-S1 transition.

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Section: Resultsmentioning

confidence: 99%

Substituent effects on the optical properties of naphthalenediimides: A frontier orbital analysis across the periodic table

Mulder

Guerra²,

Slootweg

et al. 2015

J Comput Chem

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“…The typical spectroscopic characteristic of a non‐core‐substituted NDI is absorption around 330–380 nm (assigned to the S 0 ‐S 1 transition) with typically up to three peaks present due to vibrational structure. Emission is only slightly Stokes shifted (just into the visible region) with maxima which are a mirror image of the absorption peaks (Figure ) . The maxima recorded in the absorption and emission spectra usually display small sensitivity towards solvent polarity.…”

Section: Design Strategies For Bright Ndi Moleculesmentioning

confidence: 95%

Harnessing Brightness in Naphthalene Diimides

Maniam

Higginbotham

Bell

et al. 2019

Chemistry A European J

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The development of brightly emissive compounds is of great research and commercial interest, with established and emerging applications across chemistry, biology, physics, medicine and engineering. Among the many types of molecules available, naphthalene diimides have been widely used for both fundamental photophysical studies and in practical applications that utilise fluorescence as an information readout. The monomeric naphthalene diimide is weakly fluorescent, however through various methods of core‐derivatisation, it can be developed to be highly fluorescent and further functionalised to add utility. In this review, we highlight recent advances made in naphthalene diimide chemistry that have led to development of molecules with improved optical properties, and the design strategies utilised to produce bright fluorescence emission as small molecules or in supramolecular architectures.

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“…The photophysics of N-substituted NDIs has already been investigated in detail. [22][23][24][25][26][27][28] These compounds are colorless, their first absorption band being located below 400 nm, and very weakly fluorescent because of fast intersystem crossing favored by the strong spin-orbit coupling introduced by the carbonyl groups. N-Substituted NDIs are often used as building blocks in dyads, triads, and donor-bridge-acceptor systems where they act as electron acceptor, [29][30][31][32][33] but their fast intersystem crossing prevents their use as light absorbers.…”

Section: Introductionmentioning

confidence: 99%

Ultrafast Photoinduced Charge Separation in Naphthalene Diimide Based Multichromophoric Systems in Liquid Solutions and in a Lipid Membrane

et al. 2008

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The photophysical properties of multichromophoric systems consisting of eight red or blue naphthalene diimides (NDIs) covalently attached to a p-octiphenyl scaffold, as well as a blue bichromophoric system with a biphenyl scaffold, have been investigated in detail using femtosecond time-resolved spectroscopy. The blue octachromophoric systems have been recently shown to self-assemble as supramolecular tetramers in lipid bilayer membranes and to enable generation of a transmembrane proton gradient upon photoexcitation (Bhosale, S.; Sisson, A. L.; Talukdar, P.; Fürstenberg, A.; Banerji, N.; Vauthey, E.; Bollot, G.; Mareda, J.; Röger, C.; Würthner, F.; Sakai, N.; Matile, S. Science 2006, 313, 84). A strong reduction of the fluorescence quantum yield was observed when going from the single NDI units to the multichromophoric systems in methanol, the effect being even stronger in a vesicular lipid membrane. Fluorescence up-conversion measurements reveal ultrafast self-quenching in the multichromophoric systems, whereas the formation of the NDI radical anion, evidenced by transient absorption measurements, points to the occurrence of photoinduced charge separation. The location of the positive charge could not be established unambiguously from the transient absorption measurements, but energetic considerations indicate that charge separation should occur between two NDI units in the blue systems, whereas both an NDI unit and the p-octiphenyl scaffold could act as electron donor in the red system. The lifetime of the charge-separated state was found to increase from 22 to 45 ps by going from the bi-to the octachromophoric blue systems in methanol, while a 400 ps decay component was observed in the lipid membrane. This lifetime lengthening is explained in terms of charge migration that is most efficient when the octachromophoric systems are assembled as supramolecular tetramers in the lipid membrane. Furthermore, the average charge-separated state lifetime of the red system in methanol is even larger and amounts to 750 ps. This effect cannot be simply explained in terms of Marcus inverted regime as the driving force for charge recombination in the red system is only slightly larger than in the blue one. A better spatial separation of the charges in the red system stemming from the localization of the hole on the p-octiphenyl scaffold could additionally contribute to the slowing down of charge recombination.

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Photoinduced energy–electron transfer studies with naphthalene diimides

Cited by 66 publications

References 11 publications

Substituent effects on the optical properties of naphthalenediimides: A frontier orbital analysis across the periodic table

Substituent effects on the optical properties of naphthalenediimides: A frontier orbital analysis across the periodic table

Harnessing Brightness in Naphthalene Diimides

Ultrafast Photoinduced Charge Separation in Naphthalene Diimide Based Multichromophoric Systems in Liquid Solutions and in a Lipid Membrane

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