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A series of regiochemically varied and core size extension-modulated arene- and fluoroarene-thiophene co-oligomers and the unsubstituted sexithiophene α6T were investigated theoretically to explore their electronic and optical properties. These phenylene-thiophene oligomers show great potential for application in organic light-emitting diodes (OLEDs), organic diode lasers, and organic thin-film transistors (OTFTs) because of their feasible tuning of optical and electronic properties by the various structural tunings. Density functional theory (DFT) and the ab initio HF were employed to investigate the geometric and electronic structures of the oligomers in the ground state, and the singles configuration interaction (CIS) methods were used to study the lowest singlet excited state. The lowest excitation energies (Egs), the radiative lifetime τ, and the maximal absorption/emission wavelength of the oligomers were studied within time-dependent DFT (TDDFT). All calculations were performed using the 6-31G(d) basis set. The results show that the HOMOs, LUMOs, energy gaps, ionization potentials (IPs), electron affinities (EAs), and reorganization energies are significantly affected by the various structural tunings in these co-oligomers, which is important for the improvement of the hole and electron injection into OLEDs. Interestingly, the LUMO energy of 1b, 2b, and 3b is lower than that of α6T and 1a, 2a, 3a by about 0.12 ∼ 0.47 eV, indicating that the fluorophenyl-substitution has significantly improved the electron injection properties of the oligomers. Copyright © 2008 John Wiley & Sons, Ltd. [ABSTRACT FROM AUTHOR]

The purpose of this work is to provide an in-depth investigation of the electronic and optical properties of a series of n-type conjugated oligomers, including 4-phenyl-6-(4-phenylquinolin-6-yl)quinoline (B1), 6,6′-bis(2,4-diphenylquinoline) (B1PPQ), 6,6′-bis(2-(4-tert-butylphenyl)-4-phenylquinoline) (BtBPQ), 6,6′-bis(2-p-biphenyl)-4-phenylquinoline) (B2PPQ), and 4-(6-(2-(4-aminophenyl)-4-phenylquinolin-6-yl)-4-phenylquinolin-2-yl)benzenamine (BNPPQ). The geometric and electronic structures of the oligomers in the ground state were investigated using density functional theory (DFT) and the ab initio HF, whereas the lowest singlet excited states were optimized with ab initio CIS. To assign the absorption and emission peaks observed in the experiment, we computed the energies of the lowest singlet excited states with time-dependent (TD) DFT (TD-DFT). All DFT calculations were performed using the B3LYP functional and the 6-31G basis set. The results show that the HOMOs, LUMOs, energies gaps, ionization potentials and electron affinities for each molecular are significantly affected by varying the aryl substituents, which favor the hole injection into OLEDs. The absorption and emission spectra exhibit red shifts to some extent [the absorption spectra: 335.85 (B1)< 370.63 (B1PPQ) < 376.77 (BtBPQ)< 388.67 (B2PPQ)< 412.93 nm (BNPPQ); the emission spectra: 391.48 (B1)< 430.11 (B1PPQ)< 435.86 (BtBPQ)< 444.57 (B2PPQ)< 463.28nm (BNPPQ)]. The radiative lifetimes (τ) of each oligomers are calculated as well. Because of introducing the cooperation with the electron donators such as the amidocyanogen in the common 4-phenyl-6-(4-phenylquinolin-6-yl)quinoline core for BNPPQ, which results in improving the hole-creating ability. Copyright © 2008 John Wiley & Sons, Ltd. [ABSTRACT FROM AUTHOR]

The ground and excited structures of the molecules are compared basis on the calculated by HF and CIS, respectively. The ionization potentials (IPs), electron affinities (EAs) and HOMO–LUMO gaps (ΔEHOMO–LUMO) of the oligomers are studied by the density functional theory (DFT) with B3LYP functional while the vertical excitation energies (Egs) and the maximal absorption wavelength λabs of oligomers of bifluorene and its derivatives DFE, DFA, DFBT, FDBO, and FSCHD are studied employing the time dependent density functional theory (TD-DFT) and ZINDO. Compared with BF, the derivatives DFE, DFA, and DFBT are better conjugated, easier to give an electron or a hole, as well as get an electron or a hole. Their HOMO–LUMO gaps are narrower and they have lower vertical excitation energies. The absorption and emission spectra of them are red shifting. However, FDBO and FSCHD are in the other way round. It is important that FDBO and FSCHD are good blue emitters. Copyright © 2007 John Wiley & Sons, Ltd. [ABSTRACT FROM AUTHOR]

The electronic structures and the one- and two-photon absorption (TPA) properties of two series of the olefin-linked paracyclophane (pCp) oligomers have been studied using AM1 and ZINDO-SOS methods. The relationship between the TPA cross sections and the molecular chain length is obtained. The maximum TPA cross section increases in proportion to Nα (N denotes the number of repeat units) and the values of α depend on different molecular structures. The olefin-linked pCp oligomers, which have good transparency and large TPA cross sections, are promising candidates for TPA materials. [ABSTRACT FROM AUTHOR]

Poly(fluorene)-type materials are widely used in polymer-based emitting devices. During operation there appears, however, an additional emission peak at around 2.3 eV, leading to both a color instability and reduced efficiency. The incorporation of the carbazole units has been proven to efficiently suppress the keto defect emission. In this contribution, we apply quantum-chemical techniques to investigate two series of alternating fluorene/carbazole oligomers and copolymers poly[2,7-(N-(2-methyl)-carbazole)-co-alt-2,7-m(9,9-dimethylfluorene)], namely, PFmCz (m = 1,2) and gain a detailed understanding of the influence of carbazole units on the electronic and optical properties of fluorene derivatives. The electronic properties of the neutral molecules, HOMO-LUMO gaps (ΔH-L), in addition to the positive and negative ions, are studied using B3LYP functional. The lowest excitation energies (Egs) and the maximal absorption wavelength λabs of PFmCz (m = 1,2) are studied, employing the time-dependent density functional theory (TD-DFT). The properties of the two copolymers, such as ΔH-L, Eg, IPs, and EAs were obtained by extrapolating those of the oligomers to the inverse chain length equal to zero (1/n = 0). The outcomes showed that the carbazole unit is a good electron-donating moiety for electronic materials, and the incorporation of carbazole into the polyfluorene (PF) backbone resulted in a broadened energy gap and a blue shift of both the absorption and photoluminescence emission peaks. Most importantly, the HOMO energies of PF1Cz and PF2Cz are both a higher average (0.4 eV) than polyfluorene (PF), which directly results in the decreasing of IPs of about 0.2 eV more than PF, indicating that the carbazole units have significantly improved the hole injection properties of the copolymers. In addition, the energy gap tends to broaden and the absorption and emission peaks are gradually blue-shifted to shorter wavelengths with an increase in the carbazole content in the copolymers. This is due to the interruption of the longer conjugation length of the backbone in the (F1Cz)n series. © 2005 Wiley Periodicals, Inc. J Comput Chem 26: 969–979, 2005 [ABSTRACT FROM AUTHOR]

The application of polyfluorenes in polymeric light-emitting diodes has been hampered because of the charge injection difficulties and the troublesome formation of a tailed emission band at long wavelengths (>500 nm) during device fabrication and operation, leading to both a color instability and reduced efficiency. The incorporation of the phenothiazine units has been proven to significantly enhance the hole injection and charge carrier balance and at the same time efficiently suppress the keto defect emission. In this contribution, we apply quantum-chemical techniques to investigate poly[10-(N-(2′-methyl)phenothiazine-3,7-diyl) and its fluorene copolymer poly[10-(N-(2′-methyl)-phenothiasine-3,7-diyl)-co-alt-2,7-(9,9-dimethylfluorene)] (PFPTZ) and gain a detailed understanding the influence of phenothiazine units on the electronic and optical properties of fluorene derivatives. Density functional theory (DFT) and time-dependent DFT approaches are employed to study the neutral molecules, HOMO-LUMO gaps (ΔH-L), the lowest excitation energies (Eg's), positive and negative ions, as well as the IPs and EAs, focusing on the superiority of the electronic and optical properties attributed to the introduction of electron-donating moiety phenothiazine (PTZ) through comparing with pristine polyfluorene. The outcomes show that the highly nonplanar conformation of phenothiazine ring in the ground state preclude sufficiently close intermolecular interactions essential to forming aggregates or excimers. Furthermore, the HOMO energies lift about 0.4 eV, and thus, the IPs decrease about 0.3 eV in PFPTZ, suggesting the significant improved hole-accepting and transporting abilities, due to the electron-donating properties of phenothiazine ring by the presence of electron-rich sulfur and nitrogen heteroatoms and highly nonplanar characters, resulting in the enhanced performances in both efficiency and brightness compared with pristine polyfluorene. In addition, even though the introduction of electron-donating moiety PTZ onto fluorene leads to a slight bathochromic shift in absorption and emission spectra, the copolymer still exhibited strong blue emission. [ABSTRACT FROM AUTHOR]

The electronic structures, charge injection and transport, absorption and emission spectra, properties of two series of fluorene-based oligomers {2-[2-{2-[5-(9H-Fluoren-3-yl)-thiophen-2-yl]-vinyl}-6-(2-thiophen-2-yl-vinyl)-pyran- 4-ylidene]-malononitrile} n (FTPM) n and {2-{2-{2-[5-(9H-Fluoren-2-yl)-2-hydroxy- 3-methoxy-phenyl]-vinyl}-6-[2-(2-hydroxy-3-methoxy-phenyl)-vinyl]-pyran-4- ylidene}-malononitrile} n (FOOPM) n ( n = 1–4) have been investigated by the density functional theory (DFT) approach. The ground-state geometries of (FTPM)4 and (FOOPM)4 optimized at B3LYP/6-31G(d) level exhibited zigzag arrangements. The energies of HOMO and LUMO, HOMO–LUMO energy gaps (Δ E H– L) of (FTPM) n and (FOOPM) n ( n = ∞) were obtained by linear extrapolation method. Moreover, the calculations of ionization potential (IP), electronic affinity (EA), and reorganization energy (λ) were used to evaluate the charge injection and transport abilities. For (FTPM)4 and (FOOPM)4, the TDDFT calculations revealed that the absorption peaks can be characterized as π–π* transition and couple with the location of electron density distribution changes in different repeat units. All the earlier theoretical investigations are intended to establish the structure–property relationships, which can provide guidance to design the organic light-emitting diodes (OLEDs) with high performance. [ABSTRACT FROM AUTHOR]

Ambipolar diphenylamino end-capped oligofluorenylthiophenes and fluoroarene-thiophene show great potential for application in organic light-emitting diodes (OLEDs). Here, we provide an in-depth investigation on the optical and electronic properties of OF(2)TP-NPh ( 1a), OF(2)DTP-NPh ( 2a), OF(2)TTP-NPh ( 3a), OF(2)QTP-NPh ( 4a), and 2,5-bis-(2,3,5,6-tetrafluoro-4-trifluoromethyl-phenyl)-2,2′:5′,2′′:5′′,2′′′-quaterthiophene ( 5a). The geometric and electronic structures of the oligomers in the ground-state are studied with density functional theory (DFT) and ab initio Hartree-Fock, whereas the lowest singlet excited states are optimized by ab initio CIS. The energies of the lowest singlet excited states are calculated by employing time-dependent density functional theory (TDDFT). The results show that the highest occupied molecular orbitals, lowest unoccupied molecular orbitals, energy gaps, ionization potentials, and electron affinities for the oligomers are affected by the thiophene chain length and the different end-caps. The absorption and emission spectra exhibit red shifts to some extent due to the increasing thiophene chain length and the enhancing electron-donating property of the end-caps. Furthermore, the large Stokes shifts ranging from 58 to 80 nm are examined, resulting from a more planar conformation of the excited-state between the two adjacent units in the oligomers. All the calculated data show that the fluoroarene-thiophene has improved electron transport rate and charge transfer balance performance, and all the studied molecules can be used as ambipolar-transporting materials in OLEDs. [ABSTRACT FROM AUTHOR]