Dye Aggregation Research Articles

Efficient Long-Range, Directional Energy Transfer through DNA-Templated Dye Aggregates.

The benzothiazole cyanine dye K21 forms dye aggregates on double-stranded DNA (dsDNA) templates. These aggregates exhibit a red-shifted absorption band, enhanced fluorescence emission, and an increased fluorescence lifetime, all indicating strong excitonic coupling among the dye molecules. K21 aggregate formation on dsDNA is only weakly sequence dependent, providing a flexible approach that is adaptable to many different DNA nanostructures. Donor (D)-bridge (B)-acceptor (A) complexes consisting of Alexa Fluor 350 as the donor, a 30 bp (9.7 nm) DNA templated K21 aggregate as the bridge, and Alexa Fluor 555 as the acceptor show an overall donor to acceptor energy transfer efficiency of ∼60%, with the loss of excitation energy being almost exclusively at the donor-bridge junction (63%). There was almost no excitation energy loss due to transfer through the aggregate bridge, and the transfer efficiency from the aggregate to the acceptor was about 96%. By comparing the energy transfer in templated aggregates at several lengths up to 32 nm, the loss of energy per nanometer through the K21 aggregate bridge was determined to be <1%, suggesting that it should be possible to construct structures that use much longer energy transfer "wires" for light-harvesting applications in photonic systems.

Directed Energy Transfer through DNA-Templated J-Aggregates.

Strongly coupled molecular dye aggregates have unique optoelectronic properties that often resemble those of light harvesting complexes found in Nature. The exciton dynamics in coupled dye aggregates could enhance the long-range transfer of optical excitation energy with high efficiency. In principle, dye aggregates could serve as important components in molecular-scale photonic devices; however, rational design of these coupled dye aggregates with precise control over their organization, interactions, and dynamics remains a challenge. DNA nanotechnology has recently been used to build an excitonic circuit by organizing pseudoisocyanine (PIC) dyes forming J-aggregates on the templates of poly(dA)-poly(dT) DNA duplexes. Here, the excitonic properties of the PIC J-aggregates on DNA are characterized spectroscopically in detail using poly(dA)-poly(dT) tract lengths of 24 and 48 base pairs. The excitonic properties of these DNA templated dye assemblies depend on the length and sequence of the DNA template. The incorporation of a gap of two GC base pairs between two segments of poly(dA)-poly(dT) DNA markedly reduces the delocalization of excitation in the J-aggregates. With a quantum dot (QD) as the light absorber and energy donor and using Alexa Fluor 647 (AF647) as the energy acceptor, with a DNA-templated J-aggregate in between, significant energy transfer from QD to AF647 is observed over a distance far longer than possible without the aggregate bridge. By comparing the efficiency of energy transfer through a continuous J-aggregate with the efficiency when the aggregate has a discontinuity in the middle, the effects of energy transfer within the aggregate bridge between the donor and acceptor are evaluated.

Near-Infrared-Absorbing Indolizine-Porphyrin Push–Pull Dye for Dye-Sensitized Solar Cells

Porphyrins are attractive chromophores for application in dye-sensitized solar cells (DSCs), as judicious tuning of donor-acceptor properties can enable excellent near-infrared (NIR) absorption and exceptional device performance. Here, we report a porphyrin-based dye (SM85) conjugated to the planar strong electron donor, indolizine, designed to extend absorption further into the NIR region by inducing π-π interactions such as head-to-tail dye aggregation. The optoelectronic consequences of indolizine incorporation in SM85 include raising the ground-state oxidation potential and broadening and red-shifting ultraviolet-visible-NIR absorptions, along with increased molar absorptivity when compared to the dye SM315. Density functional theory (DFT) and time-dependent DFT (TD-DFT) calculations confirm the push-pull character of SM85, which features an overlap of frontier occupied and unoccupied orbitals. Steady-state spectrophotometric analyses reveal the presence of solution aggregates via absorption and emission spectroscopies. Aggregate modes were probed by DFT and TD-DFT analyses, and plausible models are presented. SM85-based DSC devices demonstrate a 5.7% power conversion efficiency (PCE) at full sun (7.4% PCE at 10% sun) with an exceptional improvement to the incident photon-to-current conversion onset at ∼850 nm. Current dynamics measurements, time-correlated single photon counting, and computational analyses are used to better understand device performances. This study puts forward a novel intramolecular charge-transfer porphyrin system with a dramatic shift into the NIR region, as is needed for nonprecious metal-based sensitizers, and provides an example of controlled, donor-acceptor-mediated aggregation as a complementary strategy to traditional donor-acceptor modifications to single-molecule π-systems in accessing enhancements in long wavelength light harvesting in molecular-based optoelectronic devices.

Self-Assembly by Coordination with Organic Antenna Chromophores for Dye-Sensitized Solar Cells.

The development of new sensitizers and new sensitization methods is one of the important means to enhance the conversion efficiency of dye-sensitized solar cells (DSSCs); the ultimate goal is to broaden the spectral response of dyes, reduce electron recombination, and suppress dye aggregation. In this study, we have developed a series of new self-assembled dyes and applied them in DSSCs. We prepared two organic antenna chromophores S1 and S2 and coordinated them with two acceptors A1 and A2 via zinc to construct A-Zn-S series self-assembled dyes. This method is very simple and feasible and can avoid the complex synthesis steps of traditional dyes; the results show that the light-harvesting ability of devices can be improved and charge recombination can be reduced by adjusting the structures of the antenna chromophores and acceptors. The device with A2-Zn-S1 gave a power conversion efficiency of 4.25%, which was higher than those with A1-Zn-S1 (3.88%), A1-Zn-S2 (3.21%), and A2-Zn-S2 (3.52%); the main reason for this is that the different coordination combinations between the antenna chromophore and the acceptor show great differences in Voc and Jsc. The device based on A2-Zn-S1 showed a high Voc of 632 mV and a high Jsc of 9.54 mA cm-2; one reason for this is that S1 has better spectral responsiveness and another reason is that A2 has better steric resistance that effectively reduces charge recombination. Besides, IR spectra indicate that these self-assembled dyes anchored on a TiO2 surface by bicarboxyl anchoring groups are also very beneficial for improving the performance of dyes.

Optoelectronic, Aggregation, and Redox Properties of Double-Rotor Boron Difluoride Hydrazone Dyes.

We develop the chemistry of boron difluoride hydrazone dyes (BODIHYs) bearing two aryl substituents and explore their properties. The low-energy absorption bands (λmax =427-464 nm) of these dyes depend on the nature of the N-aryl groups appended to the BODIHY framework. Electron-donating and extended π-conjugated groups cause a redshift, whereas electron-withdrawing groups result in a blueshift. The title compounds were weakly photoluminescent in solution and strongly photoluminescent as thin films (λPL =525-578 nm) with quantum yields of up to 18 % and lifetimes of 1.1-1.7 ns, consistent with the dominant radiative decay through fluorescence. Addition of water to THF solutions of the BODIHYs studied causes molecular aggregation which restricts intramolecular motion and thereby enhances photoluminescence. The observed photoluminescence of BODIHY thin films is likely facilitated by a similar molecular packing effect. Finally, cyclic voltammetry studies confirmed that BODIHY derivatives bearing para-substituted N-aryl groups could be reversibly oxidized (Eox1 =0.62-1.02 V vs. Fc/Fc+ ) to their radical cation forms. Chemical oxidation studies confirmed that para-substituents at the N-aryl groups are required to circumvent radical decomposition pathways. Our findings provide new opportunities and guiding principles for the design of sought-after multifunctional boron difluoride complexes that are photoluminescent in the solid state.

Effect of Environment on Protoporphyrin IX: Absorbance, Fluorescence and Nonlinear Optical Properties.

The present study investiaged the enhancement of nonlinear optical properties of Protoporphyrin IX in photodynamic therapy using nano-droplet. To this end; absorbance, fluorescence, and nonlinear optical properties of Protoporphyrin IX were examined and results showed that dye aggregation and dielectric constant of solvent could change absorbance and fluorescence spectra. According to quantum mechanical perturbation theory, dipole moment of Protoporphyrin IX in solutions of water-ethanol was extracted. The values of nonlinear absorption and nonlinear refractive index of Protoporphyrin IX in AOT/Toluene/H2O were also reproted to be larger than aqueous solutions, due to polarity reduction of solvent as well as discount of Protoporphyrin IX aggregation in AOT/Toluene/H2O. Furthermore, the effect of cell culture media on the nonlinear optical properties of Protoporphyrin IX was analyzed and the results were compared with those of water. The photon correlation spectroscopy of solution also showed a growth in dye-droplet aggregation following the increase of Protoporphyrin IX concentration.

Wide wavelength photon harvesting in dye-sensitized solar cells utilizing cobalt complex redox electrolyte: Implication of surface passivation

A combination of near infra-red (NIR) photon harvesting and cobalt electrolytes having deeper redox energy level are needed for the fabrication of high efficiency dye-sensitized solar cells (DSSCs). A logical molecular design of unsymmetrical squaraine dye (SQ-110) as a representative of NIR dyes has been demonstrated to function well in DSSC using cobalt complex redox electrolyte. Problem of mass transport limitations due to the bulky cobalt complex ions leading to relatively enhanced charge recombination was amicably solved by single as well as multiple compact metal oxide surface passivation on both of the transparent conducting oxide substrate as well as mesoporous TiO2. Complete absence of light absorption beyond 550 nm wavelength region by D-35 and utilization of a complementary light harvesting dye SQ-110 led to efficient wide wavelength photon harvesting. DSSC fabricated using a dye cocktail of D-35 and SQ-110 in 4:1 ratio resulted in to photoconversion efficiency (PCE) of 7.2%, which is much higher as compared to the constituent individual sensitizers D-35 (3.6%) and SQ-110 (1.9%). This synergistic enhancement in PCE by dye cocktail was associated with the mutual co-operation of respective dyes in terms controlling the dye aggregation and complementary photon harvesting. In this dye cocktail system, D-35 is involved in the prevention of dye aggregation, lower wavelength photon harvesting and energy transfer induced photocurrent enhancement.

Tunable Induced Circular Dichroism in Thin Organic Films

In this work, we study the induced optical activity (OA) of spin-coated molecular films made of a pristine optically inactive laser dye (Rhodamine 110) in the visible range. The OA is brought about by a “transparent” chiral modifier (1,1′-Bi-2-naphthol). For the first time, it was experimentally shown how two separate mechanisms yield induced circular dichroism (ICD) in such a film and how they are describable through a model. In one, ICD occurs via a direct interaction between dye and modifier molecules. In the other, ICD takes place in optical transitions of present dye aggregates. It is proposed that this is caused by a chiral bias through an enantiomeric excess in inherently chiral and optically active dye aggregates promoted by the chiral modifier in a sergeant-soldier manner. Further, the strength of ICD strongly depends on the ratio between the modifier and the dye as well as on the preparation conditions. The resulting high tunability of the OA paired with a straightforward film preparation opens ...

Adsorption of polyelectrolytes onto the oppositely charged surface of tubular J-aggregates of a cyanine dye

The adsorption of three different polycations at the negatively charged surface of tubular J-aggregates of the amphiphilic cyanine dye 3,3′-bis(2-sulfopropyl)-5,5′,6,6′-tetrachloro-1,1′-dioctylbenzimidacarbocyanine (C8S3) is investigated by means of cryogenic electron microscopy and optical absorption spectroscopy. All three polycations could be adsorbed at the tubular aggregates without flocculation or precipitation when added in molar amounts of monomers sufficiently smaller than that of the dye molecules. It is found that preferably, a minority of aggregates is coated by the polycations while a majority of aggregates is left uncoated. For the coated aggregates, the adsorption leads to charge reversal of the aggregate surface as supported by zeta potential measurements. The morphology of the coating differs significantly for the three polycations: The branched polycation polyethylenimine (PEI) attaches to the tubular aggregate by hit-and-stick adsorption of the coiled state in solution forming irregular clot-like coatings; the flexible and weakly cationic poly (allylamine hydrochloride) (PAH) forms a more homogeneous coating but destroys the integrity of the dye aggregate; the more hydrophobic and strong polycation poly (diallyldimethylammonium chloride) (PDADMAC) forms a thin and homogeneous layer, supposedly by wrapping around the tubular aggregate. For the latter growth of a second double layer of dyes is observed for the aggregates. The different morphologies of the coating layers are explained by the details of the chemical structure of the polycations. The possible adsorption of polyelectrolytes at these amphiphilic tubular structures, stabilized by means of hydrophobic forces, is far from obvious and demonstrates an applicable route to the build-up of more complex nanostructures in solution by means of a self-assembly process.

Concentration-dependent dye aggregation and disassembly triggered by the same artificial helical foldamer

Abstrct Constructing and regulating the cyanine dye aggregates have been constantly pursued because of their wide applications in photosensitizers, biological fluorescence probes, nonlinear optics, etc. However, to realize such a process using a single additive still remains a formidable challenge. Here, the aggregation and disassembly of positively charged 3,3-diethyloxadicarbocyanine iodide (DiOC2(5)) have been demonstrated just by changing the concentration of an artificial poly(phenylenediethynylene)-based helical foldamer (Poly-1) bearing L-alanine sodium pendants with an amide linker. Poly-1 possessed the negatively charged pendants and hydrophobic helical grooves. Upon simple mixing of equal DiOC2(5) and Poly-1, DiOC2(5) molecules were mainly enriched on Poly-1 surface driven by electrostatic interaction and arranged along the main chain of Poly-1, resulting in the formation of chiral H-aggregates. But, the excessive Poly-1 would attract some DiOC2(5) molecules in H-aggregates via electrostatic interaction. The isolated monomers were easy to orderly disperse into the helical grooves due to hydrophobic interaction. Meanwhile, during the aggregation and disassembly, the solution color changed from peachblow to purple red and then to purple and finally to navy blue.

Improving the effective photovoltaic performance in dye-sensitized solar cells using an azobenzenecarboxylic acid-based system

In this research, an azobenzenecarboxylic acid was used as a sufficient co-adsorbent in combination with N719 dye. As it is found from the results, an optimized concentration of the co-absorbent leads to the highest efficiency. The dye-sensitized solar cells (DSSCs) parameters such as short-circuit current (Jsc), open-circuit voltage (Voc) and conversion efficiency (η) were obtained -14.87 mA/cm2, 0.765 V and 5.20% respectively. Based on the results, the N719/Azobenzenecarboxylic-based system shows a significant increase in Voc and Jsc, resulting in an ∼21% improvement in the efficiency. A higher conversion efficiency for the co-adsorbent-based systems was assigned to their enhanced η, which is attributed to reduced dye aggregation, higher electron injection and increased Voc. This corresponded to the improved electron density in the TiO2 conduction band of the photoanode and reduced charge recombination revealed through electrochemical impedance spectroscopy measurements. Also, evidence was provided for a long charge life time and a high resistance of charge recombination for the co-absorbed solar cells.

Role of hexyloxy groups in zinc phthalocyanines bearing sulfonic acid anchoring groups for dye-sensitized solar cells

Zinc phthalocyanine dyes bearing four sulfonic acid anchoring groups with (A-ZnPc) and without (H-ZnPc) four chloro and eight hexyloxy groups were used as sensitizers for dye-sensitized solar cells (DSSCs). The dyes were investigated in terms of their optical, electrochemical and photovoltaic properties. The presence of these groups in dye A-ZnPc resulted in both red-shifted absorption and decreased dye aggregation, which are beneficial for the improvement of device performance. In the presence of chenodeoxycholic acid (CDCA) as a coadsorbent, the DSSC based on H-ZnPc shows a power conversion efficiency (PCE) of 0.96%, which is improved by [Formula: see text]40% as compared to the device without CDCA. However, the PCE of an A-ZnPc-based device with CDCA slightly enhances from 1.15% (without CDCA) to 1.22%, indicating that the bulky hexyloxy groups with large steric hindrance can effectively suppress aggregation of the adsorbed dye. The results showed that the zinc phthalocyanine dye bearing bulky hexyloxy groups is a promising candidate to construct efficient coadsorbent-free DSSCs.

Fluorescence Turn-on Synthetic Lipid Rafts on Supramolecular Sheets and Hierarchical Concanavalin A Assembly.

Here we report fluorescence turn-on synthetic lipid rafts by self-assembly of a cationic distyrylanthracene derivative on a negatively-charged sheet in an aqueous solution. First, the negatively-charged 2D membrane structure is formed by lateral associations of aromatic rods with carboxylate groups. Then, the synthetic rafts are floated on the surface of the negatively-charged sheets through electrostatic interactions. The fluorescence of the synthetic rafts is turned on due to the aggregation of the positively-charged AIE dye on the sheets, facilitating monitoring of the formation of rafts. Concanavalin A (Con A) protein can load hierarchically onto the synthetic rafts at neutral pH to provide discrete Con A aggregates with a uniform size of ≈12 nm. The uniform aggregates of Con A on the synthetic rafts can stimulate Jurkat cells with enhanced efficiency, as compared with random-sized aggregates of Con A.

Control of Porphyrin Dye Aggregation Using Bis(4-pyridyl)Alkanes in Dye Sensitized Solar Cells

The aggregation of sensitizer molecules on the surface of photoanode is a serious issue that can affect the photovoltaic performance of dye-sensitized solar cells. Prevention of dye agglomeration, therefore, is critical. Traditional methods of aggregation control are either synthetically challenging or technologically difficult and expensive. In this article, the use of bis(4-pyridyl)alkanes to control porphyrin dye aggregation is presented. Three bis(4-pyridyl)alkanes – bis(4-pyridyl)butane L4, bis(4-pyridyl)octane L8 and bis(4-pyridyl)decane L10 were synthesized. These bis(4-pyridyl)alkane ligands are axially attached to the metallic center of synthesized porphyrin dye P. The complexes was obtained by mixing the solutions of dye P and each ligand (L) in 2:1 ratio 1 h before the soaking step. As a result three cells were prepared: P-L4, P-L8 and P-L10. The performance of these cells were compared with a reference cell which was prepared from porphyrin dye P only. IPCE analysis demonstrated the highest dye load in P-L4 cell which was ascribed to lowered dye aggregation. Photovoltaic analysis showed improved short circuit current density due to suppressed dye aggregation caused by the complexation of the porphyrin dye P with the linker L4. As a result the overall cell efficiency increased to 42% demonstrating the successful utilization of the (4-pyridyl)alkane linker complexes with porphyrin dye.

Self-Assembled "Off/On" Nanopomegranate for In Vivo Photoacoustic and Fluorescence Imaging: Strategic Arrangement of Kupffer Cells in Mouse Hepatic Lobules.

Kupffer cells (KCs), potent scavenger cells located in hepatic sinusoids, constantly phagocytize and degrade foreign materials to maintain metabolism and clearance. Understanding the strategic KC arrangement which links to their spatial location and function in hepatic lobules, the basic functional unit in the liver, is highly valuable for characterizing liver function. However, selectively labeling KCs and characterizing their function in vivo remains challenging. Herein, a fast self-assembled pomegranate structure-like nanoparticle with "nanopomegranate seeds" of dye aggregates has been developed, which has dual-modality "off/on" capability. This nanopomegranate shows good photostability, a high extinction coefficient, a high KC labeling efficiency (98.8%), and better visualization of KC morphology than commercial FluoSpheres. In vivo photoacoustic (PA) and fluorescence imaging consistently visualize that KCs are strategically distributed along the central vein (CV)-portal triad (PT) axis in each liver lobule: more and larger KCs exist in areas closer to the PTs. The high-resolution PA quantitative data further revealed that the density of KCs was linearly dependent on the r n/ rmax ratio (their relative location along the CV-PT axis) ( R2 = 0.7513), and the KC density at the outermost layer is almost 246-fold that at the innermost layer (each layer is 8 μm). Notably, the phagocytic ability of KCs located in layers with r n/ rmax ratios of 0.167-0.3 varies in a zigzag pattern, as evidenced by their different PA intensities. Additionally, the fluorescence imaging quantitation suggests similar fluorescence activation of nanopomegranate in KCs. Nanopomegranates combined with dual-modality imaging reveal the strategic arrangement of KCs in vivo, greatly extending our understanding of liver physiology.

Phenothiazine dye featuring encapsulated insulated molecular wire as auxiliary donor for high photovoltage of dye-sensitized solar cells by suppression of aggregation

Two efficient dye-sensitized solar cells have been fabricated by two novel D–D–π–A phenothiazine-based organic dyes (PH2 and PH3) with an encapsulated insulated molecular wire (EIMW) as an auxiliary donor. The cell sensitized by PH2 with EIMW as an auxiliary donor shows a much higher photovoltage (Voc) relative to the reference dye PH1 without EIMW, because the former dye can inhibit dye aggregation and suppress the charge recombination effectively. The results show that the cell sensitized by PH2 with co-adsorption of chenodeoxycholic acid obtains a high power conversion efficiency, even higher than that of the cell based on N719. Thus, an effective way to increase the photovoltage and efficiency of the DSSCs has been developed by introducing the EIMW into the organic dyes due to the effective inhibition of dye aggregation and charge recombination.

Non-Kasha Behavior in Quadrupolar Dye Aggregates: The Red-Shifted H-Aggregate

Aggregates of quadrupolar DAD-type chromophores are investigated theoretically using the essential states model (ESM) enhanced to include vibronic coupling. On the basis of vibronic signatures in the absorption and photoluminescence spectra, important connections are made to the Frenkel exciton model, which is the basis for defining conventional H- and J-aggregates. In contrast to the exciton theory, the ESM allows for an unusual type of the red-shifted H-aggregate, driven by the large quadrupole–quadrupole interaction. Except for the red shift of the main absorption peak, such aggregates display all of the characteristics of conventional H-aggregates, including suppressed radiative decay rates and all of the vibronic signatures in the absorption and photoluminescence spectra consistent with Frenkel exciton models. Red-shifted H-dimers occur for a range of slip angles, which separate conventional H- and J-aggregate behavior, with the slip range diminishing with increasing intermolecular separation. Davydo...

Interchromophoric Interactions Determine the Maximum Brightness Density in DNA Origami Structures.

An ideal point light source is as small and as bright as possible. For fluorescent point light sources, homogeneity of the light sources is important as well as that the fluorescent units inside the light source maintain their photophysical properties, which is compromised by dye aggregation. Here we propose DNA origami as a rigid scaffold to arrange dye molecules in a dense pixel array with high control of stoichiometry and dye-dye interactions. In order to find the highest labeling density in a DNA origami structure without influencing dye photophysics, we alter the distance of two ATTO647N dyes in single base pair steps and probe the dye-dye interactions on the single-molecule level. For small distances strong quenching in terms of intensity and fluorescence lifetime is observed. With increasing distance, we observe reduced quenching and molecular dynamics. However, energy transfer processes in the weak coupling regime still have a significant impact and can lead to quenching by singlet-dark-state-annihilation. Our study fills a gap of studying the interactions of dyes relevant for superresolution microscopy with dense labeling and for single-molecule biophysics. Incorporating these findings in a 3D DNA origami object will pave the way to bright and homogeneous DNA origami nanobeads.

DNA G-Quadruplexes as a Template To Direct Cyanine Dyes To Form H-Aggregates and Application of the Self-Assembly Entity as a New G-Quadruplexes Ligands Screening Platform.

The organization of organic chromophores to form H-/J-aggregates can result in new biomaterials with unique properties and applications. DNA-template self-assembly is one of the most attractive strategies to guide the formation of chromophore aggregates. However, the DNA templates are mainly limited to canonical nucleic acids structures [single (ss)- and double (ds)-stranded DNA]. DNA G-quadruplexes (GQs), with distinct and various structural features, were rarely exploited to guide the formation of dye aggregates. In this study, we present the spontaneous assembly of cyanine dye IR786 to form H-aggregates on DNA GQs exclusively, but no IR786 aggregates formed by adjusting the experimental parameters or on ss-/ds-DNA. Furthermore, on the basis of the assembly entity (GQs-IR786), an adaptive GQs-FID (fluorescence intercalator displacement) assay for screening of GQs ligands was developed. In contrast with the existing GQs-FID screening schemes, this assay displayed attractive performance in many aspects (such as turn-on signal output, broad screening range, and time saving). All these results have undoubtedly demonstrated the great values of DNA GQs as a template to guide the formation of dye aggregates. We hope that more GQs structures would be exploited as templates to expand the variety of functional materials in the future. Moreover, the specifically formed H-aggregates of IR786 on GQs are significant for GQs' detection, and we also expect that this GQs-FID assay would be further studied and finally applied to screen GQs ligands in a high-throughput manner in the future.

Unclogging electron-transporting channels via self-assembly for improving light harvesting and stability of dye-sensitized solar cells

Two nitrogen-rich heterocycle donor dyes, NP-2 and NP-3, have been strategically designed and synthesized to construct functionalized self-assembly layers. Through the formation of N⋯H hydrogen bonds between these nitrogen-rich heterocycle donors and 4-tert-butylbenzoic acid (PTBBA), the electron leak points (imine group (N)) may be plugged, thus blocking excited-state electron lateral transferring between the adsorbed dyes and electron leaking from electron-transporting channel into the electrolyte. Furthermore, the huge 3-dimensional sizes of such supramolecule sensitizers can not only suppress dye aggregation, but enhance the photoresponse capacity in visible region. Therefore, the devices based on NP-2@PTBBA and NP-3@PTBBA, which obtained by the cocktail sensitization procedures, can be improved by increasing the open-circuit photovoltage (Voc) without any loss of the short-circuit photocurrent density (Jsc) owing to the synergy effect between self-assembly and co-sensitization. Although the device based on NP-3/PTBBA via the stepwise sensitization procedure delivers lower efficiency, it can remain at 103.14% of the initial efficiency as a result of parallel increase in Jsc and Voc values. Overall, the design principles provide a clear road map of supramolecular dye-sensitized solar cells (SDSSCs) and demonstrate the potential of 1,3,5-triazine-based dyes in solar cells research.