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Near-Infrared Phosphorescent Hybrid Organic-Inorganic Perovskite with High-Contrast Dielectric and Third-Order Nonlinear Optical Switching Functionalities.

ABSTRACT: Hybrid organic-inorganic perovskites providing integrated functionalities for multimodal switching applications are widely sought-after materials for optoelectronics. Here, we embark on a study of a novel pyrrolidinium-based cyanide perovskite of formula (C₄H₁₀N)₂KCr(CN)₆, which displays thermally driven bimodal switching characteristics associated with an order-disorder phase transition. Dielectric switching combines two features important from an application standpoint: high permittivity contrast (Δε' = 38.5) and very low dielectric losses. Third-order nonlinear optical switching takes advantage of third-harmonic generation (THG) bistability, thus far unprecedented for perovskites and coordination polymers. Structurally, (C₄H₁₀N)₂KCr(CN)₆ stands out as the first example of a three-dimensional stable perovskite among formate-, azide-, and cyanide-based metal-organic frameworks comprising large pyrrolidinium cations. Its stability, reflected also in robust switching characteristics, has been tracked down to the Cr³⁺ component, the ionic radius of which provides a large enough metal-cyanide cage for the pyrrolidinium cargo. While the presence of polar pyrrolidinium cations leads to excellent switchable dielectric properties, the presence of Cr³⁺ is also responsible for efficient phosphorescence, which is remarkably shifted to the near-infrared region (770 to 880 nm). The presence of Cr³⁺ was also found indispensable to the THG switching functionality. It is also found that a closely related cobalt-based analogue doped with Cr³⁺ ions displays distinct near-infrared phosphorescence as well. Thus, doping with Cr³⁺ ions is an effective strategy to introduce phosphorescence as an additional functional property into the family of cobalt-cyanide thermally switchable dielectrics.

SUBMITTER: Ma Czka M

PROVIDER: S-EPMC8762641 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Project description:In the present investigation, quantum chemical calculations have been performed in a systematic way to explore the optoelectronic, charge transfer, and nonlinear optical (NLO) properties of different bis(dicyanomethylene) end-functionalized quinoidal oligothiophenes. The effect of different conformations (linking modes of thiophene rings) on conformational, optoelectronic, and NLO properties are studied from the best-performed dimer to octamer. The optical and NLO properties of all the selected systems (1-7) are calculated by means of density functional theory (DFT) methods. Among all the designed compounds, the largest linear isotropic (αiso) polarizability value of 603.1 × 10-24 esu is shown by compound 7 which is ∼12, ∼16, ∼9, ∼11, ∼10, and ∼4 times larger as compared to compounds 1-6, respectively. A relative investigation is performed considering the expansion in third-order NLO polarizability as a function of size and conformational modes. Among all the investigated systems, system 7 shows the highest value of static second hyperpolarizability ⟨γ⟩ with an amplitude of 7607 × 10-36 esu at the M06/6-311G** level of theory, which is ∼521, ∼505, ∼38, ∼884, ∼185, and ∼15 times more than that of compounds 1-6, respectively. The extensively larger ⟨γ⟩ amplitude of compound 7 with higher oscillator strength and lower transition energy indicates that NLO properties are remarkably dependent upon linking modes of thiophene rings and its chain length. Furthermore, to trace the origin of higher nonlinearities, TD-DFT calculations are also performed at the same TD-M06/6-311G** level of theory. Additionally, a comprehensive understanding of the effect of structure/property relationship on the NLO polarizabilities of these investigated quinoidal oligothiophenes is obtained through the inspection of Frontier molecular orbitals, the density of states (TDOS and PDOS), and molecular electrostatic potential diagrams including the transition density matrix. Hence, the current examination will not just feature the NLO capability of entitled compounds yet additionally incite the interest of experimentalists to adequately modify the structure of these oligothiophenes for efficient optical and NLO applications.

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Near-Infrared Phosphorescent Hybrid Organic-Inorganic Perovskite with High-Contrast Dielectric and Third-Order Nonlinear Optical Switching Functionalities.

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