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Synthesis and Emergent Photophysical Properties of Diketopyrrolopyrrole-Based Supramolecular Self-Assembly.

ABSTRACT: Diketopyrrolopyrrole (DPP)-based molecular semiconductors exhibit intriguing optical and charge transport properties. Herein, we rationally design a series of electronically identical but structurally distinct Hamilton receptor (HR)-based supramolecular assembly of DPP. The HR endows supramolecular assemblies via hydrogen bonding with enhanced structural ordering and excitonic couplings. The mechanism of supramolecular self-assembly was probed by diffusion ordered spectroscopy (DOSY) nuclear magnetic resonance (NMR) and solid-state IR spectroscopy studies. We investigated the morphology of self-assembly, photophysical and electrochemical properties and compared them with the identical DPP molecular structures without HRs. The microstructure of self-assembly was probed with atomic force microscopy in thin films. Subsequently, the influence of solid-state packing was studied by single-crystal X-ray diffraction. The single-crystal structure of HR-TDPP-C₂₀ reveals slipped stack arrangements between the two neighboring chromophores with π-π stacking distance and slip angle of 3.55 Å and 35.4°, respectively. Notably, the slight torsional angle of 1° between thiophene and lactam rings and small π-π stacking distance suggest a significant intermolecular coupling between thiophene (D) and lactam (A) rings. This intramolecular coupling between two π-π chromophore stacks manifests in their optical properties. In this manuscript, we report rational design and synthesis of supramolecular self-assembly of DPP with a collection of compelling structural and optical properties.

SUBMITTER: Maity N

PROVIDER: S-EPMC9280760 | biostudies-literature | 2022 Jul

REPOSITORIES: biostudies-literature

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Synthesis and Emergent Photophysical Properties of Diketopyrrolopyrrole-Based Supramolecular Self-Assembly.

Maity Nilabja N Majumder Kanad K Patel Arun Kumar AK Swain Diptikanta D Suryaprakash Nagarajarao N Patil Satish S

ACS omega 20220630 27

Diketopyrrolopyrrole (DPP)-based molecular semiconductors exhibit intriguing optical and charge transport properties. Herein, we rationally design a series of electronically identical but structurally distinct Hamilton receptor (HR)-based supramolecular assembly of DPP. The HR endows supramolecular assemblies via hydrogen bonding with enhanced structural ordering and excitonic couplings. The mechanism of supramolecular self-assembly was probed by diffusion ordered spectroscopy (DOSY) nuclear mag ...[more]

PMID: 35847286

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Project description:In the present study, the influence of the hydrogen bonding for the one- and two-photon absorption of the prototypical squaraine dye is investigated with quantum chemistry tools. The central squaraine unit is bound by strong hydrogen bonds with 4-substituted N,N'-diphenylurea and, alternatively, N,N'-diphenylthiourea molecules, which affects to a high extend the properties of the squaraine electron accepting moiety, thus shifting its maximum absorption wavelength and enhancing the TPA cross section. The replacement of oxygen by sulfur atoms in the squaraine central ring, known to affect its photophysical behavior, is considered here as the way of modifying the strength and nature of the intermolecular contacts. Additionally, the influence of the oxygen-by-sulfur replacement is also considered in the N,N'-diphenylurea moiety, as the factor affecting the acidity of the N-H protons. The introduction of the sequence of the substituents of varying electron-donating or electron-withdrawing characters in the position 4 of N,N'-diphenyl(thio)urea subsystems allows to finely tune the hydrogen bonding with the central squaraine unit by further modification of the N-H bond characteristics. All of these structural modifications lead to the controlled adjustment of the electron density distribution, and thus, the properties affected such as transition moments and absorption intensity. Ab initio calculations provide strong support for this way of tailoring of one- or two-photon absorption due to the obtained strong hypsochromic shift of the maximum one-photon absorption wavelength observed particularly for thiosquaraine complexes and an increase in the TPA wavelength together with the increase in the TPA cross section. Moreover, the source of the strong modification of the thiosquaraine OPA in contrast to the pristine oxosquaraine upon N,N'-diphenyl(thio)urea substitution is determined. Furthermore, for the first time, the linear dependence of the non-additivity in the interaction energy on the Hammett substituent constant is reported. The stronger the electron-donating character of the substituent, the larger the three-body non-additive components and the larger their percentage to the total interaction energy.

Dataset Information

Synthesis and Emergent Photophysical Properties of Diketopyrrolopyrrole-Based Supramolecular Self-Assembly.

Publications

Synthesis and Emergent Photophysical Properties of Diketopyrrolopyrrole-Based Supramolecular Self-Assembly.

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