Nature of intermolecular interaction in squaraine dimers

Kaczmarek‐Kędziera, Anna; Żuchowski, Piotr S.; Kędziera, Dariusz

doi:10.1038/s41598-020-76631-z

Cited by 8 publications

(7 citation statements)

References 46 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Interaction energy decomposition for the exemplary bent dimer 1-H indicated the strong influence of the dispersion energy component (dispersion-to-electrostatic ratio equal to 2.52, dispersion-governed interaction). This value is similar to the dispersion energy component observed in the prototypical squaraine dimers [41], where for the stacked dimers depending on the mutual monomer displacement it amounts to −46.45 or −51.51 kcal/mol for long and short displacement, respectively. Among the other analyzed systems that are important in the context of aggregation, the benzoxathiazole seem to attract dispersively stronger, while the benzooxadiazole exhibit slightly weaker dispersion interaction than 1-H.…”

Section: Meso-substituted Bodipy Derivativessupporting

confidence: 84%

BODIPY dimers: structure, interaction, and absorption spectrum

Rybczyński

Kaczmarek‐Kędziera

2021

Struct Chem

View full text Add to dashboard Cite

The object of the present study are BODIPY molecules obtained previously by Piskorz et al. (Dyes Pigm. 178:108322, 2020) for their antimicrobial activity. Structural analysis of the BODIPY dimers is presented in context of the aggregation influence on the photophysical properties. The thorough investigation of the nature of intermolecular interaction in the representative BODIPY dimers is provided together with the decomposition of the interaction energy into the components of well-defined origin according to SAPT procedure. For the model BODIPY systems the careful examination of the interaction nature for the dimer structure based on experimental crystal study as well as fully optimized is given. The tendencies observed in the model dimers are further on investigated for two pairs of BODIPY systems designed for biomedical application. The analyzed molecules are shown to maximize the mutual interaction by the optimization of the stacking dispersion contacts between the aromatic rings of the molecules, therefore producing stable dimers. The estimation of SAPT0 interaction energy components confirms the dominating dispersion character arising from mutual BODIPY core contacts. The influence of the dimerization process on the photophysical properties of the systems studied theoretically depends to the high extend on the dimerization mode and is significant for parallel and antiparallel dispersion-governed dimers.

show abstract

Section: Meso-substituted Bodipy Derivativessupporting

confidence: 84%

BODIPY dimers: structure, interaction, and absorption spectrum

Rybczyński

Kaczmarek‐Kędziera

2021

Struct Chem

View full text Add to dashboard Cite

show abstract

“…An unusual aggregation system deviating significantly from the basic J- and H-picture is found for certain squaraine dyes. Due to their unique and easily customizable optical properties , this large family of π-conjugated quadrupolar molecules has attracted attention in recent experimental ,− and theoretical studies. − As reported, the molecules can easily form either J- or H-type aggregates depending on their molecular structure ,, and sample preparation conditions. ,,, Moreover, squaraines with a symmetric molecular backbone show strong electron-donating and -accepting properties, and both intra- and inter-molecular charge transfer could play an important role in the optical spectra of squaraine aggregates . Recently, a family of n -alkyl aniline squaraines (see Figure a) was synthesized and engineered , for organic solar cells which can reach relatively high power conversion efficiencies.…”

Section: Introductionmentioning

confidence: 99%

Structural Disorder as the Origin of Optical Properties and Spectral Dynamics in Squaraine Nano-Aggregates

et al. 2022

View full text Add to dashboard Cite

In contrast to regular J-and H-aggregates, thin film squaraine aggregates usually have broad absorption spectra containing both J-and H-like features, which are favorable for organic photovoltaics. Despite being successfully applied in organic photovoltaics for years, a clear interpretation of these optical properties by relating them to specific excited states and an underlying aggregate structure has not been made. In this work, by static and transient absorption spectroscopy on aggregated n-butyl anilino squaraines, we provide evidence that both the red-and blue-shifted peaks can be explained by assuming an ensemble of aggregates with intermolecular dipole−dipole resonance interactions and structural disorder deriving from the four different nearest neighbor alignments�in sharp contrast to previous association of the peaks with intermolecular charge-transfer interactions. In our model, the next-nearest neighbor dipole−dipole interactions may be negative or positive, which leads to the occurrence of J-and Hlike features in the absorption spectrum. Upon femtosecond pulse excitation of the aggregated sample, a transient absorption spectrum deviating from the absorbance spectrum emerges. The deviation finds its origin in the excitation of two-exciton states by the probe pulse. The lifetime of the exciton is confirmed by the band integral dynamics, featuring a single-exponential decay with a lifetime of 205 ps. Our results disclose the aggregated structure and the origin of red-and blue-shifted peaks and explain the absence of photoluminescence in squaraine thin films. Our findings underline the important role of structural disorder of molecular aggregates for photovoltaic applications.

show abstract

“…These dyes have in their general structure two-electron donor groups on both sides of the squaric acid core as an electron acceptor group (10,11). This zwitterionic structure, together with the rigidity and planarity conferred by the central ring, leads the squaraine dyes to present absorption in the visible to NIR range, high molar extinction coefficients, good photoconductivity, good chemical/photochemical stability, moderate fluorescence quantum yields and long fluorescence lifetime (12)(13)(14)(15).…”

Section: Introductionmentioning

confidence: 99%

Squaraine Dyes Derived from Indolenine and Benzo[e]indole as Potential Fluorescent Probes for HSA Detection and Antifungal Agents

Gomes

Ferreira

Boto

et al. 2022

Photochem & Photobiology

View full text Add to dashboard Cite

Four squaraine dyes derived from 2,3,3-trimethylindolenine and 1,1,2-trimethyl-1H-benzo[e]indole with different combinations of barbituric groups attach to the central ring, having ester groups and alkyl chains in the nitrogen atoms of heterocyclic rings were synthesized. These dyes were fully characterized, and their photophysical behavior was studied in ethanol and phosphate-buffered solution. Absorption and emission bands between 631 and 712 nm were detected, with the formation of aggregates in aqueous media, which is typical of this class of dyes. Tests carried out with 1,3diphenylisobenzofuran allowed us to verify the ability of the dyes to produce singlet oxygen. The interaction of synthesized dyes with human serum albumin (HSA) was also evaluated, being demonstrated a linear correlation between fluorescence intensity and protein concentration. The antifungal potential of the dyes against the yeast Saccharomyces cerevisiae was evaluated using a broth microdilution assay. In order to test the photosensitizing capacity of the synthesized dyes, tests were carried out in the dark and with irradiation, using a custom-built light-emitting diode that emits close to the absorption wavelength of the studied dyes. The results showed that the interaction of dyes with HSA and the antifungal activity depends on the different structural modifications of the dyes.

show abstract

Nature of intermolecular interaction in squaraine dimers

Cited by 8 publications

References 46 publications

BODIPY dimers: structure, interaction, and absorption spectrum

BODIPY dimers: structure, interaction, and absorption spectrum

Structural Disorder as the Origin of Optical Properties and Spectral Dynamics in Squaraine Nano-Aggregates

Squaraine Dyes Derived from Indolenine and Benzo[e]indole as Potential Fluorescent Probes for HSA Detection and Antifungal Agents

Contact Info

Product

Resources

About