1088205-02-0Relevant articles and documents
Intersystem Crossing in Naphthalenediimide–Oxoverdazyl Dyads: Synthesis and Study of the Photophysical Properties
Hussain, Mushraf,Taddei, Maria,Bussotti, Laura,Foggi, Paolo,Zhao, Jianzhang,Liu, Qingyun,Di Donato, Mariangela
, p. 15615 - 15627 (2019)
Oxoverdazyl (Vz) radical units were covalently linked to the naphthalenediimide (NDI) chromophore to study the effect of the radical on the photophysical properties, especially the radical enhanced intersystem crossing (REISC), which is a promising approach to develop heavy-atom-free triplet photosensitizers. Rigid phenyl or ethynylphenyl linkers between the two moieties were used, thus REISC and formation of doublet (D1, total spin quantum number S=1/2) and quartet states (Q1, S=3/2) are anticipated. The photophysical properties of the dyads were studied with steady-state and femtosecond/nanosecond transient absorption (TA) spectroscopies and DFT computations. Femtosecond transient absorption spectra show a fast electron transfer (1→D0 decay, and the slow decay component (2.0 μs; 20 %) to the Q1→D0 ISC. DFT computations indicated ferromagnetic interactions between the radical and chromophore (J=0.07–0.13 eV). Reversible formation of the radical anion of the NDI moiety by photoreduction of the radical-NDI dyads in the presence of sacrificial electron donor triethanolamine (TEOA) is achieved. This work is useful for design of new triplet photosensitizers based on the REISC effect.
Influences of the number of 2-ethylhexylamine chain substituents on electron transport characteristics of core-substituted naphthalene diimide analogues
Birajdar, Shailesh S.,Naqvi, Samya,More, Kerba S.,Puyad, Avinash L.,Kumar, Rachana,Bhosale, Sidhanath V.,Bhosale, Sheshanath V.
, p. 1590 - 1600 (2021)
We designed and synthesized a series of naphthalenediimide (NDI) derivatives through core-substitution (coded as cNDI) with various number of 2-ethyl-hexylamine (EHA) chains at different positions. The molecular structure of cNDI derivatives such as cNDI-1EHA, cNDI-2EHA, cNDI-3EHA and cNDI-4EHA bearing one, two, three and four 2-ethyl-hexylamine chains, respectively, was confirmed by different spectroscopic techniques such as FTIR, 1H-NMR, 13C-NMR spectroscopy and mass spectrometry. Interestingly, the incorporation of different numbers of 2-ethyl-hexylamine on electron-deficient cNDI yields diverse photophysical and electrochemical properties. The change in the number of alkyl chains on the NDI core significantly influences the redox properties and the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energy levels. The changes in the morphology of the spin-coated films before and after annealing are reorganized differently depending on the number of 2-ethyl-hexylamine topology proved by scanning electron microscopy (SEM) and X-ray diffraction (XRD) techniques. The electron mobility of cNDIs was examined by following the standard protocol of the space-charge limiting current (SCLC) method. The NDI derivatives bearing various number of 2-ethyl-hexylamine chains at the NDI core after thermal treatment at 170 °C exhibited very good electron mobility of the order of 10-6 to 10-4 cm2 V-1 s-1. The observed electron mobility trends depend not only on the number of 2-ethyl-hexylamine substituents but also on the changes in thin-film morphology.
Low and High Molecular Mass Dithienopyrrole–Naphthalene Bisimide Donor–Acceptor Compounds: Synthesis, Electrochemical and Spectroelectrochemical Behaviour
Rybakiewicz, Renata,Glowacki, Eric D.,Skorka, Lukasz,Pluczyk, Sandra,Zassowski, Pawel,Apaydin, Dogukan Hazar,Lapkowski, Mieczyslaw,Zagorska, Malgorzata,Pron, Adam
, p. 2839 - 2851 (2017)
Two low molecular weight electroactive donor–acceptor–donor (DAD)-type molecules are reported, namely naphthalene bisimide (NBI) symmetrically core-functionalized with dithienopyrrole (NBI-(DTP)2) and an asymmetric core-functionalized naphthalene bisimide with dithienopyrrole (DTP) substituent on one side and 2-ethylhexylamine on the other side (NBI-DTP-NHEtHex). Both compounds are characterized by low optical bandgaps (1.52 and 1.65 eV, respectively). NBI-(DTP)2undergoes oxidative electropolymerization giving the electroactive polymer of ambipolar character. Its two-step reversible reduction and oxidation is corroborated by complementary EPR and UV/Vis–NIR spectroelectrochemical investigations. The polymer turned out to be electrochemically active not only in aprotic solvents but also in aqueous electrolytes, showing a distinct photocathodic current attributed to proton reduction. Additionally, poly(NBI-(DTP)2) was successfully tested as a photodiode material.
N-Type Water/Alcohol-Soluble Naphthalene Diimide-Based Conjugated Polymers for High-Performance Polymer Solar Cells
Wu, Zhihong,Sun, Chen,Dong, Sheng,Jiang, Xiao-Fang,Wu, Siping,Wu, Hongbin,Yip, Hin-Lap,Huang, Fei,Cao, Yong
, p. 2004 - 2013 (2016)
With the demonstration of small-area, single-junction polymer solar cells (PSCs) with power conversion efficiencies (PCEs) over the 10% performance milestone, the manufacturing of high-performance large-area PSC modules is becoming the most critical issue for commercial applications. However, materials and processes that are optimized for fabricating small-area devices may not be applicable for the production of high-performance large-area PSC modules. One of the challenges is to develop new conductive interfacial materials that can be easily processed with a wide range of thicknesses without significantly affecting the performance of the PSCs. Toward this goal, we report two novel naphthalene diimide-based, self-doped, n-type water/alcohol-soluble conjugated polymers (WSCPs) that can be processed with a broad thickness range of 5 to 100 nm as efficient electron transporting layers (ETLs) for high-performance PSCs. Space charge limited current and electron spin resonance spectroscopy studies confirm that the presence of amine or ammonium bromide groups on the side chains of the WSCP can n-dope PC71BM at the bulk heterojunction (BHJ)/ETL interface, which improves the electron extraction properties at the cathode. In addition, both amino functional groups can induce self-doping to the WSCPs, although by different doping mechanisms, which leads to highly conductive ETLs with reduced ohmic loss for electron transport and extraction. Ultimately, PSCs based on the self-doped WSCP ETLs exhibit significantly improved device performance, yielding PCEs as high as 9.7% and 10.11% for PTB7-Th/PC71BM and PffBT4T-2OD/PC71BM systems, respectively. More importantly, with PffBT4T-2OD/PC71BM BHJ as an active layer, a prominent PCE of over 8% was achieved even when a thick ETL of 100 nm was used. To the best of our knowledge, this is the highest efficiency demonstrated for PSCs with a thick interlayer and light-harvesting layer, which are important criteria for eventually making organic photovoltaic modules based on roll-to-roll coating processes.
Tricomponent Supramolecular Multiblock Copolymers with Tunable Composition via Sequential Seeded Growth
Agasti, Sarit S.,Das, Angshuman,George, Subi J.,Sarkar, Aritra,Sasmal, Ranjan,Venugopal, Akhil
, p. 18209 - 18216 (2021)
Synthesis of supramolecular block co-polymers (BCP) with small monomers and predictive sequence requires elegant molecular design and synthetic strategies. Herein we report the unparalleled synthesis of tri-component supramolecular BCPs with tunable microstructure by a kinetically controlled sequential seeded supramolecular polymerization of fluorescent π-conjugated monomers. Core-substituted naphthalene diimide (cNDI) derivatives with different core substitutions and appended with β-sheet forming peptide side chains provide perfect monomer design with spectral complementarity, pathway complexity and minimal structural mismatch to synthesize and characterize the multi-component BCPs. The distinct fluorescent nature of various cNDI monomers aids the spectroscopic probing of the seeded growth process and the microscopic visualization of resultant supramolecular BCPs using Structured Illumination Microscopy (SIM). Kinetically controlled sequential seeded supramolecular polymerization presented here is reminiscent of the multi-step synthesis of covalent BCPs via living chain polymerization. These findings provide a promising platform for constructing unique functional organic heterostructures for various optoelectronic and catalytic applications.
Tuning the optical and electrochemical properties of core-substituted naphthalenediimides with styryl imide substituent
Fernando, Roshan,Etheridge, Forrest,Muller, Evan,Sauvé, Geneviève
, p. 2506 - 2514 (2015)
The effect of styryl imide substitution on optical and electrochemical properties of core-substituted naphthalenediimides was examined by synthesizing a series of naphthalenediimide molecules. 2-Ethylhexylamino and 5-(2-ethylhexyl)thiophene groups were used as core substituents. The optical and electrochemical properties of styryl imide substituted compounds were compared with other imide substitutions including hydrogen, 2-ethylhexyl, and 4-thienylphenyl. Generally, the imide substituents had little effect on the optical properties, except when the combination of alkylamino core and styryl imide substituents was used. In this latter case, we observed a 104 nm red-shift of the absorption onset upon film formation, resulting in an unusually broad visible absorption (500-800 nm) for these types of molecules. This is explained by the planarity of the molecule and the formation of intermolecular aromatic donor-acceptor type interactions. These results show that imide substituents play a role in tuning opto-electronic properties of NDI molecules, and that NDI molecules with styryl imide substituents merit further evaluation for opto-electronic applications.
Room-temperature long-lived triplet excited states of naphthalenediimides and their applications as organic triplet photosensitizers for photooxidation and triplet-triplet annihilation upconversions
Guo, Song,Wu, Wanhua,Guo, Huimin,Zhao, Jianzhang
, p. 3933 - 3943 (2012)
Naphthalenediimide (NDI) derivatives with 2,6- or 2,3,6,7-tetrabromo or amino substituents were prepared. N,N'-dialkyl-2,6-dibromo NDI (compound 2) and N,N'-dialkyl-2,3,6,7-tetrabromo NDI (compound 4) show phosphorescence emission at 610 or 667 nm, respectively. Phosphorescence was never observed for NDI derivatives. Conversely, N,N'-dialkyl-2,6-dibromo-3,7-diamino NDI (compound 5) shows strong absorption at 526 nm and fluorescence at 551 nm, and no phosphorescence was observed. However, nanosecond time-resolved transient difference absorption spectroscopy confirmed that the triplet excited state of 5 was populated upon photoexcitation. 2,3,6,7-Tetraamino NDI (6) shows fluorescence, and no triplet excited state was populated upon excitation. The compounds were used as singlet oxygen (1O2) photosensitizers for the photooxidation of 1,5-dihydroxylnaphthalene (DHN). We found that 5 is more efficient than the conventional photosensitizer, such as Ir(ppy)2(bpy)[PF6]. The compounds were also used as organic triplet photosensitizers for triplet-triplet annihilation based upconversions. An upconversion quantum yield up to 18.5% was observed.
Naphthalimide unit derivative-based small molecular receptor material, and preparation method and application thereof
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Paragraph 0036-0039, (2021/02/20)
The invention belongs to the field of organic photovoltaic materials, and particularly relates to a naphthalimide unit derivative-based small molecule acceptor material and a preparation method thereof, and the naphthalimide unit derivative-based small molecule acceptor material is used as an active layer to be applied to an organic solar cell device or a photoelectric detector. A small molecularphotovoltaic material with high thermal stability and excellent electron transport performance is obtained by coupling a plurality of donor unit central nucleuses with a mono-substituted naphthalimideunit derivative. The material can be applied to industrial production of organic solar cells and photoelectric detectors.
