Weak Donor Research Articles

Enhanced Luminescence of Dye-Decorated ZIF-8 Composite Films via Controllable D-A Interactions for White Light Emission.

Metal-organic frameworks (MOFs) constructed by metal ions/clusters and organic linkers are used to encapsulate fluorescent guest species with aggregation-caused quenching (ACQ) effects to enhance fluorescence properties due to their porous structures and high specific surface areas. However, there would be a problem of matching between MOF pores and guest molecules' sizes. In this paper, amorphous ZIF-8 was modified by carboxyl functional groups (H3BTC-ZIF-8) via introducing the 1,2,4-benzenetricarbonic acid (H3BTC) ligand into the ZIF-8 sol system. Moreover, H3BTC-ZIF-8 was used for the loading of organic fluorescent dyes rhodamine 6G (R6G) and coumarin 151 (C151) to prepare R6G/C151/H3BTC-ZIF-8 composite films. A white-light-emitting composite film (R6G/C151/H3BTC-ZIF-8) with CIE coordinates of (0.323, 0.347) was successfully prepared by compounding fluorescent dyes (R6G and C151) with H3BTC-modified ZIF-8, whose photoluminescence quantum yield (PLQY) can reach 64.0%. It was higher than the PLQY of the composite films prepared by crystalline ZIF-8 (40.2%) or amorphous ZIF-8 without H3BTC (48.0%) compounded with the same concentrations of dyes. The fluorescence enhancement was probably attributed to an increased amount of active sites of H3BTC-modified ZIF-8 interacting with dyes C151 and R6G. This can form hydrogen bonds between H3BTC-ZIF-8 and C151, and weak electron donor-acceptor (D-A) interactions between H3BTC-ZIF-8 and R6G molecules, respectively, thus enhancing the interactions between dyes and ZIF-8 and reducing the ACQ effect existing between dye molecules. Therefore, this strategy could provide an important guidance to develop white-light-emissive materials.

Highly Efficient Blue Electro‐Fluorescence and Hybrid White Electroluminescence Basing on a Novel Hybrid Local and Charge‐Transfer (HLCT) Material with Weak Donor–Acceptor Structure and High Carrier Mobilities

AbstractHigh efficiency and luminance are critical for commercialized blue organic light‐emitting diodes (OLEDs). Herein, a novel donor–acceptor (D–A) blue‐emissive molecule with a weak donor and acceptor is synthesized. The moderate hybrid local and charge transfer (HLCT) state character endows PPIBPO with blue fluorescence and high quantum efficiency. More importantly, the rigid, rod‐like molecular structure gives rise to the regularity of the stacking pattern of PPIBPO, which enables its extraordinary carrier mobilities in non‐doped OLED, the hole mobility and electron mobility are as high as 5.09 × 10−5 cm2 V−1 s−1 and 3.22 × 10−4 cm2 V−1 s−1, respectively. The non‐doped blue OLED of PPIBPO achieves a maximum external quantum efficiency (EQE) of 12.0% and a maximum luminance of 55023 cd m−2, which is one of the best values among the non‐doped blue OLEDs based on HLCT molecules. Furthermore, high‐efficiency two‐color hybrid warm white OLED with a maximum EQE up to 22.5% and maximum power efficiency of 87.0 lm W−1 is also achieved using PPIBPO as blue‐fluorophor.

Expanding the scope of bis(catecholato)germane catalysis: hydrosilylation, hydroboration, Friedel-Crafts alkylation and oligomerization.

Various applications of bis(catecholato)germanes in catalysis were examined. The hydrosilylation of benzaldehydes, hydroboration of phenylacetylene derivatives, and Friedel-Crafts alkylation using arylalkenes and either diphenylamine or anisole was achieved. Furthermore, the recently reported oligomerization of α-methylstyrene catalyzed by bis(catecholato)germanes with weak donor ligands was examined further. The formation of a trimer species was observed in DCM. VTNA and Hammett analyses of the oligomerization reaction were conducted and an updated mechanism for bis(catecholato)germane catalysis is proposed.

Molecular torsion controls the excited state relaxation pathways of multibranched tetraphenylpyrazines: effect of substitution of morpholine vs. phenoxazine.

Multibranched donor-acceptor derivatives exhibiting desirable photophysical properties are efficiently used in optoelectronic devices, in which the excited state relaxation dynamics of the derivatives control the efficiency of the devices. Here, the effect of intramolecular torsion on the excited state relaxation dynamics of tetraphenylpyrazine (TPP) derivatives in non-polar (toluene) and polar (THF) solvents is investigated by substituting the electron donor of morpholine (TPP-4MOP) and phenoxazine (TPP-4PHO) leading to the planar and twisted configurations, respectively, using femtosecond and nanosecond transient absorption spectroscopy. In the steady state, TPP-4MOP showed feeble emission (ΦF ∼0.03) due to the weak donor by the delocalization of electron density supported by theoretical optimization. The TPP-4PHO exhibited strong emission (ΦF ∼0.18) in toluene compared to that in THF, in which it showed a large Stokes shift (∼9691 cm-1) with low fluorescence quantum yield (ΦF ∼0.01). The observation of large Stokes shifts, inherent nature and theoretical calculations of TPP-4PHO suggest the twisting of the dihedral angle between tetraphenylpyrazine and phenoxazine in the excited state leading to the twisted intramolecular charge transfer state (TICT). The femtosecond and nanosecond transient absorption and picosecond time-resolved emission spectra of TPP-4PHO revealed the signature of the existence of both the partial TICT and TICT states in THF leading to the triplet state. Whereas in the case of TPP-4MOP, the transient absorption spectra showed the formation of the triplet state from the local excited state without the involvement of the TICT state. Aggregation studies of TPP-4PHO in a THF and water mixture reflect the elimination of the TICT state by the restriction of intramolecular torsion in the aggregates leading to an increase of 12-fold of the fluorescence intensity along with shifting of the maximum towards the blue region. These studies revealed that the excited state relaxation pathways of the derivatives are controlled by polarity-dependent torsional motion.

Sensitive turn-off detection of nitroaromatics using fluorescent tetraphenylethylene phosphonate derivative

The derivatisation of tetraphenylethylene is broadly utilized to synthesize molecular sensor for detecting explosives among other analytes, the effects of such alteration have been little investigated. Herein, we report the sensing of various nitro phenols using fluorescence signals produced by (4-(1, 2, 2-tris (4-phosphonophenyl) vinyl) phenyl) phosphonic acid octasodium salt (TPPE). It is observed that the fluorescence of TPPE at 411 nm and 432 nm are quenched in the presence 2,4,6-trinitrophenol (TNP) via electron transfer between weak TPE donor and acceptor mechanism. Moreover, TPPE – TNP association is based on non-covalent interaction including hydrogen-bonding and electrostatic interactions. TPPE shows strong binding affinity and selectivity towards TNP over various other nitroaromatic analytes. The sensing detection limit (LOD) towards TNP is 4.58 × 10−9 M. In detailed molecular simulation experiments are performed to investigate the non-covalent interaction, oscillation frequency, possible transitions and energy levels of molecular complexation between TPPE and TNP. This study supports the sensing mechanism of TPPE towards TNP, suggesting suitable interaction mode between the receptor and PA.

Nitrenium Salts in Intramolecular Lewis Pairs

AbstractHerein we present the synthesis, full characterization and systematic investigation of intramolecular Lewis pairs incorporating Lewis acidic N‐heterocyclic nitrenium salts linked to phosphine Lewis bases. Intramolecular Lewis adducts and frustrated Lewis pairs (FLPs) were obtained, depending on different modification to the molecular structure. Several different aryl and alkyl groups were utilized as substituents on the core naphthotriazinium and phosphine components, which were linked by an alkyl chain of variable length. Whereas an intermolecular Lewis adduct of nitrenium with a relatively weak phosphine donor (Ph2PMe) was not observed, the corresponding intramolecular version (Ph2PR) was detected both in a dissociated Lewis pair form and as a coordinated Lewis adduct simultaneously. Additionally, one set of modifications led to a unique rearrangement of the nitrenium core, resulting in a fused heterocycle. The mechanism of this rearrangement was analyzed computationally.

Non-Covalent Interactions in Weak Donor–Acceptor Systems Based on Toluene and Tetracyanoquinodimethane Derivatives

Non-Covalent Interactions in Weak Donor–Acceptor Systems Based on Toluene and Tetracyanoquinodimethane Derivatives

A DFT/TDDFT Investigation on Fluorescence and Electronic Properties of Chromone Derivatives.

The development of quick and precise detection technologies for active compounds in vivo is critical for disease prevention, diagnosis and pathological investigation. The fluorescence signal of the fluorophore usually defines the probe's sensitivity to the chemical being examined. Many natural compounds containing flavone and isoflavone scaffolds exhibit a certain amount fluorescence, albeit with poor fluorescence quantum yields. Therefore, we used density functional theory (DFT) and time-dependent density functional theory (TDDFT) calculations to investigate the fluorescence characteristics of chromium-derived fluorophores in more depth. Different substituents are introduced at different positions of the chromone. As weak electron donor groups, alkyl and aromatic groups were discovered to have varying quantum yields on the fluorophore scaffold, and longer alkyl chains are favorable to enhance fluorescence quantum yield. In comparison to the amino group, substituted amino group can avoid group rotation, and the introduction of cyclic amines such as pyrrolidine and heterocyclic amines can improve optical characteristics. The electron-donating methoxy group at position 6 helps to increase the fluorescence quantum yield.

Stacking Interactions: A Supramolecular Approach to Upgrade Weak Halogen Bond Donors.

The co-crystallization of tetracyanobenzene (TCB) with haloarenes ArX provided six new co-crystals TCB ⋅ ArX (ArX=PhCl, PhBr, 4-MeC6 H4 Cl, 4-MeC6 H4 Br, 4-MeOC6 H4 Cl, 1,2-Br2 C6 H4 ) which were studied by X-ray diffraction. In these systems, the strong collective effect of π⋅⋅⋅π stacking interactions and lone pair-(X)⋅⋅⋅π-hole-(C) bondings between TCB and ArX promote the strength of X⋅⋅⋅Ncyano halogen bonding (HaB). Theoretical studies showed that the stacking interactions affect the σ-hole depth of the haloarenes, thus significantly boosting their ability to function as HaB donors. According to the molecular electrostatic potential calculations, the σ- hole-(Cl) value (1.5 kcal/mol) in the haloarene 4-MeOC6 H4 Cl (featuring an electron-rich arene moiety and exhibiting very poor σ-hole-(Cl) ability) increases significantly in the stacked trimer (TCB)2 ⋅ 4-MeOC6 H4 Cl (12.5 kcal/mol). Theoretical DFT calculations demonstrate the dramatic increase of X⋅⋅⋅Ncyano HaB strength for stacked trimers in comparison with parent unstacked haloarenes.

3,4-Bis-O-propargyl-1,2:5,6-di-O-isopropylidene-D-mannitol: a study of multiple weak hydrogen bonds in the solid state.

The title homochiral compound, C18H26O6, 1, was examined by single-crystal X-ray crystallography in order to understand its potential as a synthetic building block, particularly in inter- and intramolecular cyclocondensation reactions. It has also proven to be an excellent model for understanding multiple weak donor-acceptor D-H...A interactions involving terminal acetylenes as donors and as acceptors. The asymmetric unit of 1 comprises three almost identical independent molecules, each with the mannitol 2R,3R,4R,5R configuration and different conformations. Like independent molecules align in strands through acetylenic donor C-H...O contacts with equivalent dioxolanyl acceptor groups. Two of the strands are aligned unidirectionally, in parallel, while the third strand aligns perpendicular to the first two, to give interwoven layers in the supramolecular structure. A detailed study of the interdigitation of the second propargyl group from each independent molecule between strands, and of other short interstrand C-H...O contacts, provides new insight into the application of weak hydrogen-bond theory within the context of a conformationally flexible symmetrical molecule. Analyses of the Cambridge Structural Database using Crystal Packing Features and ConQuest search motifs support the importance of the D...A distance parameter, demonstrate the different influences of donor and acceptor types, and reveal the interplay between H...A and D...A contributions in different contact types.

Synthesis, Structure, and Bonding of a XeIV Transition-Metal Coordination Complex, F3 XeFb - - -WOF4.

The coordination complex, F3 XeFb - - -WOF4 , was synthesized in CFCl3 solvent by reaction of the weak fluoride-ion donor and strong oxidative fluorinating agent, XeF4 , with the moderate-strength fluoride-ion acceptor, WOF4 . The compound is the only transition-metal coordination complex of XeIV and was characterized at low temperatures by single-crystal X-ray diffraction and Raman spectroscopy. Xenon tetrafluoride and WOF4 coordinate trans to the W=O bond through a W- - -Fb bond. The XeF3 moiety of F3 XeFb - - -WOF4 acquires a degree of [XeF3 ]+ character upon coordination that is reflected by its Xe-F stretching frequencies which are intermediate with respect to those of XeF4 and [XeF3 ]+ . Calculations show W- - -Fb is predominantly an electrostatic, σ-hole bond with a significant orbital contribution that accounts for the bent Xe-Fb - - -W angle. The calculations show F3 XeFb - - -MOF4 (M=Cr, Mo) are less stable than their W analogue, consistent with failed attempts to synthesize F3 XeFb - - -MoOF4 .

Intermolecular Interactions in G Protein-Coupled Receptor Allosteric Sites at the Membrane Interface from Molecular Dynamics Simulations and Quantum Chemical Calculations.

Allosteric modulators are called promising candidates in G protein-coupled receptor (GPCR) drug development by displaying subtype selectivity and more specific receptor modulation. Among the allosteric sites known to date, cavities at the receptor–lipid interface represent an uncharacteristic binding location that raises many questions about the ligand interactions and stability, the binding site structure, and how all of these are affected by lipid molecules. In this work, we analyze interactions in the allosteric sites of the PAR2, C5aR1, and GCGR receptors in three lipid compositions using molecular dynamics simulations. In addition, we performed quantum chemical calculations involving the symmetry-adapted perturbation theory (SAPT) and the natural population analysis to quantify the strength of intermolecular interactions. We show that besides classical hydrogen bonds, weak polar interactions such as O–HC, O–Br, and long-range electrostatics with the backbone amides contribute to the stability of allosteric modulators at the receptor–lipid interface. The allosteric cavities are detectable in various membrane compositions. The availability of polar atoms for interactions in such cavities can be assessed by water molecules from simulations. Although ligand–lipid interactions are weak, lipid tails play a role in ligand binding pose stability and the size of allosteric cavities. We discuss physicochemical aspects of ligand binding at the receptor–lipid interface and suggest a compound library enriched by weak donor groups for ligand search in such sites.

Supramolecular structural influences from remote functionality in coordination complexes of 4-picolylamine ligands

A series of nine cobalt(II), copper(II) and silver(I) coordination complexes of structurally similar picolylamine ligands, N-(4-picolyl)piperidine (L1) and N-(4-picolyl)morpholine (L2), have been prepared and analyzed. These consist of a dinuclear copper(II) complex [Cu2(OAc)4(L1)2] (1), tetranuclear copper(II) complexes [Cu4OCl6(L1)4]·MeCN·H2O (2) and [Cu4OCl7(L2)2 (L2H)]·2MeCN·9H2O (3), trichlorocobaltate complexes [CoCl3 (L1H)]·MeCN (4) and [CoCl3(L2H)] (5), silver coordination polymers poly-[AgL1]SbF6·0.5THF) (6), poly-[Ag(L2)]SbF6·0.5THF (7) and poly-[Ag(L1)(CO2CF3)] (9) and discrete dinuclear silver complex [Ag2(L2)2(THF)4](SbF6)2 (8). While the coordination and classical N–H···X hydrogen bonding in these species is related and largely independent of backbone functionality, differences in ligand composition dictate the d weak interactions and the supramolecular structure. In 1, 2, 4, 6 and 9 piperidine acts as a weak hydrogen bond donor, with C–H···Cl/O/F contacts mostly observed from the methylene groups adjacent to the amine. In the morpholine species 3, 5, 7 and 8 the tendency for morpholine to associate via reciprocated C–H···O interactions overrides the other crystal packing tendencies, changing both the local and extended structures. By studying both strong and weak packing interactions, this study presents a test case for the design of discrete and polymeric coordination compounds with finely tuned modes of intermolecular interaction.

Solution-processed deep-blue fluorophores based on phenanthroimidazole integrated with benzimidazole with HLCT character for efficient deep-blue organic light emitting devices

Organic light-emitting diodes (OLEDs) has been used extensively in the field of display technology because of their advantageous features for the next-generation displays. However, the development of efficient deep-blue emitters with Commission International de l’Eclairage CIEy <0.1 is very rare. In this context, we have designed and synthesized two efficient deep blue emitters PTPIBI and m-CF3PIBI by incorporating weak donor phenanthroimidazole (PI) and weak acceptor benzimidazole (BI) to study their potential application in deep-blue organic electronic devices. The systematic investigation of photophysical and theoretical properties of the both the fluorophores indicate that the materials possesses locally excited (LE) and charge transfer (CT) excited states character. The synthesized emitters showed high thermal stability and intense blue emission with high quantum yields. Hence, we have fabricated solution-processed undoped and doped OLED devices with newly synthesized emitters and observed that the PTPIBI demonstrated the superior performance as compared to that of m-CF3PIBI. The best electroluminescent (EL) performance is displayed by the device fabricated with PTPIBI (5 wt% in the Tris(4-carbazoyl-9-ylphenyl)amine (TCTA) host), showing a maximum external quantum efficiency (EQE) of 2.4%, CIE coordinates of (0.15, 0.08) and maximum luminance of 2507 cd/m2.

New wide band gap π-conjugated copolymers based on anthra[1,2-b: 4,3-b': 6,7-c''] trithiophene-8,12-dione for high performance non-fullerene polymer solar cells with an efficiency of 15.07 %

Developing efficient wide-bandgap copolymer donor materials to match with narrow bandgap non-fullerene acceptors is continuously ongoing for polymer solar cells. Herein, two new D-A copolymers are designed and synthesized by embedding the same anthra[1,2-b:4,3-b':6,7-c"] trithiophene-8,12-dione (A3T) acceptor unit and different donor units, i.e., BDTTZ ( P126 ) and BDTTh ( P127 ). These copolymers showed broad absorption from 350 to 680 nm and deeper HOMO energy level. We have used these two copolymers as donors and a narrow bandgap non-fullerene acceptor Y6 to prepare bulk heterojunction polymer solar cells (PSCs). After the optimization, P126 :Y6 and P127 :Y6 attained overall power conversion efficiency of 15.07% and 12.27%, respectively. The higher PCE for the P126 than P127 is associated with the more efficient photon harvesting and photogenerated excitons, balanced charge transport, and low energy loss. Our results may help to design new polymers with a deeper highest occupied molecular orbital level that will be well-matched with non-fullerene acceptors. • We have used the approach of weak donor and strong acceptor approach to design the D-A copolymers. • Two D-A copolymers were designed with same A3T acceptor and different donors, i.e., BDTTZ ( P126 ) and BDTTh (P127 ). • Both the copolymers showed deeper HOMO energy level to achieved high V OC . • P126 :Y6 and P127 :Y6 showed power conversion efficiency of 15.07% and 12.27%, respectively.

Inner-sphere and outer-sphere charge-transfer quenching of the uranyl UO22+(VI) luminescence, and kinetics for the tertiary and secondary alcohols activated uranyl emission

For the uranyl UO22+(VI) luminescence, the quenching constants (Kq: mM−1) of various σ–donors and π–donors, which have been shown to form electron-donor–acceptor (EDA) complexes with UO22+, were found directly related to the ionization energies (IE: eV) of the electron donors, such that the common logarithm logKq = –0.0932(IE) + 1.671 (R2 = 0.945). The relationship has revealed an inner-sphere mechanism for the quenching resulting from the charge-transfer (a single-electron transfer) from the HOMO of the quenching substance (Q) to a SOMO of the excited state (UO22+)* that takes place in an EDA [Q, (UO22+)*] complex. For some weak electron donors which do not form EDA complexes with UO22+, their Kq values for the quenching of UO22+ luminescence were found significantly much smaller than expected from the logKq versus IE relationship established for the inner-sphere charge-transfer quenching. The observations have indicated an outer-sphere charge-transfer quenching mechanism possibly resulting from the simple collision between the quenching substance and UO22+ without the formation of an EDA complex between them. In the presence of tertiary butyl alcohol (tBuOH) at 0 – 0.015 M (15 mM), the intensity (I) of the emission of UO22+ (0.01 M) at 508 nm (with Ex = 340 nm) in acetone was found to increase linearly as a function of the tBuOH millimolar concentration (mM) (I = 34.2[tBuOH] + 1802, R2 = 0.992). Kinetic analysis has revealed an electronic energy transfer from the excited state of tBuOH (A*), identified by luminescence spectroscopy, to the ground state of UO22+ (U) to promote it to the excited state (U*) (A* + U → A + U*), enhancing the UO22+ luminescence. The excitation energy transfer is believed to follow a Dexter mechanism, with the overall spin of the energy donor and acceptor conserved, followed by an intersystem crossing ([1A*, 1U] → [1A, 1U*] → [1A, 3U*]).

Novel Azocoumarin Derivatives-Synthesis and Characterization.

The paper presents synthesis and characterization of nine new thiazolyl-(phenyldiazenyl)-2H-chromen-2-one dyes. The impact of substituent structure in thiazole ring in the synthesized azocoumarin derivatives on electrochemical properties, photoisomerization process and photovoltaic response was examined. The dyes were electrochemically active and undergo reduction and oxidation processes. They showed low electrochemically estimated energy band gap in the range of 1.71–2.13 eV. Photoisomerization process of the synthesized molecules was studied in various solvents such as ethanol, chloroform and N,N-dimethylformamide (DMF) upon the UV illumination. It was found that novel azodyes showed reversible trans-cis-trans isomerization and exhibited long thermal back to the trans form, that was even 7 days in DMF. Selected azocoumarin were molecularly dispersed in polystyrene for preparation of guest-host azopolymer systems to study the cis-trans thermal isomerization of obtained dyes in solid state. The photovoltaic activity of the azochromophores was tested in bulk-heterojunction solar cells. They acting as weak donors in device with structure ITO/PEDOT:PSS/dye:PC70BM/Al. No photovoltaic response of cells with azocoumarin derivatives bearing 4-fluorobenzene, 3,4-dichlorobenzene, or 4-(1-adamantyl) unit was found. Additionally, dye which showed the best activity was examined in three-component solar cells ITO/PEDOT:PSS/PTB7:PC70BM:dye/PFN/Al.

Synthesis and Characterization of Hypercoordinated Silicon Anions: Catching Intermediates of Lewis Base Catalysis.

Anionic hypercoordinated silicates with weak donors were proposed as key intermediates in numerous silicon‐based reactions. However, their short‐lived nature rendered even spectroscopic observations highly challenging. Here, we characterize hypercoordinated silicon anions, including the first bromido‐, iodido‐, formato‐, acetato‐, triflato‐ and sulfato‐silicates. This is enabled by a new, donor‐free polymeric form of Lewis superacidic bis(perchlorocatecholato)silane 1. Spectroscopic, structural, and computational insights allow a reassessment of Gutmann's empirical rules for the role of silicon hypercoordination in synthesis and catalysis. The electronic perturbations of 1 exerted on the bound anions indicate pronounced substrate activation.

Synthesis and Characterization of Hypercoordinated Silicon Anions: Catching Intermediates of Lewis Base Catalysis

AbstractAnionic hypercoordinated silicates with weak donors were proposed as key intermediates in numerous silicon‐based reactions. However, their short‐lived nature rendered even spectroscopic observations highly challenging. Here, we characterize hypercoordinated silicon anions, including the first bromido‐, iodido‐, formato‐, acetato‐, triflato‐ and sulfato‐silicates. This is enabled by a new, donor‐free polymeric form of Lewis superacidic bis(perchlorocatecholato)silane 1. Spectroscopic, structural, and computational insights allow a reassessment of Gutmann's empirical rules for the role of silicon hypercoordination in synthesis and catalysis. The electronic perturbations of 1 exerted on the bound anions indicate pronounced substrate activation.

Donor Functionalization Tuning the N‐Type Performance of Donor–Acceptor Copolymers for Aqueous‐Based Electrochemical Devices

AbstractIn this work, three n‐type donor–acceptor copolymers consisting of glycolated naphthalene tetracarboxylicdiimide (gNDI) coupled with variable donating companion moieties are reported. Using 2,2′‐bis(3,4‐ethylenedioxy)bithiophene, 2,​2′‐​bithiophene, 3,3′‐difluoro‐2,2′‐bithiophene (FBT), the donating strength of the donor units is systematically functionalized. These copolymers are used as a platform for aqueous‐based electrochemical devices, including energy‐storage devices, electrochromic devices (ECDs), and organic electrochemical transistors (OECTs). It is found that the electrochemical redox stability and electron mobility of copolymers are significantly improved via weakening the electron‐donating strength of donor units. gNDI coupling with FBT (gNDI‐FBT) exhibits a charge‐storage capacity exceeding 190 Fg−1, which is the highest value reported to date for NDI‐based polymer electrodes in aqueous media. For ECDs, gNDI‐FBT remains 100% of initial electrochromism contrast (∆%T = 20%) up to 1200 s. In addition, gNDI‐FBT outperforms its two analogs in OECTs, including lower threshold voltage (0.19 V), faster response time (45.5 ms), and higher volumetric capacitance (197 F cm−3). Moreover, gNDI‐FBT with fluorine atoms leads to the bipolarons delocalization along the polymer backbone and favorable molecular packing for ion–electron transport. Through such weak donor functionalization strategy, this work provides ways for n‐type copolymers tuning to access desirable performance metrics in optical, electrochemical, and bioelectronic applications.