Supramolecular Rotor:  Adamantylammonium([18]crown-6) in [Ni(dmit)<sub>2</sub>]<sup>-</sup> Salt

Sato, Daisuke; Akutagawa, Tomoyuki; Takeda, Sadamu; Noro, Shin Ichiro; Nakamura, Takayoshi

doi:10.1021/ic061831u

Cited by 44 publications

(12 citation statements)

References 26 publications

(16 reference statements)

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“…This was shown to result in remarkable electronic properties of functionalized adamantane monolayers . Moreover, the high symmetry and dynamic nature of functionalized adamantane analogues have been explored for use as functional elements of plastic crystals and molecular machines, such as supramolecular rotors, however their utility in layered perovskites remains uncertain …”

Section: Resultsmentioning

confidence: 99%

“…[12] We have introduced A, which features an adamantane core equipped with a CH 2 NH 3 + group (Figure 1b, bottom) into the FA-based layered perovskite composition. [16][17][18] Moreover, the high symmetry and dynamic nature of functionalized adamantane analogues have been explored for use as functional elements of plastic crystals and molecular machines, such as supramolecular rotors, [19] however their utility in layered perovskites remains uncertain. [13][14][15] This was shown to result in remarkable electronic properties of functionalized adamantane monolayers.…”

Section: Supramolecular Designmentioning

confidence: 99%

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Supramolecular Engineering for Formamidinium‐Based Layered 2D Perovskite Solar Cells: Structural Complexity and Dynamics Revealed by Solid‐State NMR Spectroscopy

Milić

Kubicki

et al. 2019

Advanced Energy Materials

149

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represent a class of materials described by the general formula S 2 Y n−1 M n X 3n+1 , where S (typically C m H 2m+1 NH 3 + ) and Y (typically methylammonium (MA), formamidinium (FA), or their mixtures) are organic cations, M is a divalent metal cation (Pb 2+ , Sn 2+ ), and X is a halide ion (Br − , I − ). RPPs form layered structures of perovskite-like slabs separated by the organic ammonium cation spacers (S), where the value of n represents the number of layers of [MX 6 ] 4− octahedra in the stack (Figure 1a; n = 1-3). These structural features render the RPPs natural quantum wells where the number of layers in conjunction with the nature of the spacer group determines the optoelectronic properties. [1][2][3] While MA-based layered perovskite compositions have been extensively explored, [3,5,6] reports of FA-based layered perovskites remain scarce despite the better stability of the FA cation. [7][8][9] In addition, unlike their 3D analogues, layered 2D perovskites generally suffer from poor solarto-electric power conversion efficiencies, [1][2][3] particularly for the FA-based layered perovskites reported to date. Despite the ongoing effort, some of the best performing MA-based layered 2D perovskites have exceeded efficiencies of 12% with hotcasting techniques, [3] whereas the present FA-based analogues gave efficiencies around 1% for various compositions, reaching over 6% after extensive treatments. [7][8][9] This relatively poor performance of RPPs can be predominantly attributed to the inhibition of charge transport by the organic cations that act as insulating layers, since it is the inorganic domains that mainly contribute to the conductivity of the system. [1] Moreover, RPPs possess higher exciton binding energies, which result in decreased performance owing to inefficient exciton dissociation, and in turn to short-circuit photocurrent losses. [3,5] This has been counterbalanced by using additives, such as thiourea, [7][8][9] or employing hot-casting fabrication techniques, [1] with limited reproducibility as well as lack of operational stability reports.Here, we consider that these limitations on the performance of RPPs might be overcome by exploiting the potential tunability of the inherent structural properties through the design Perovskite solar cells are one of the most promising photovoltaic technologies, although their molecular level design and stability toward environmental factors remain a challenge. Layered 2D Ruddlesden-Popper perovskite phases feature an organic spacer bilayer that enhances their environmental stability. Here, the concept of supramolecular engineering of 2D perovskite materials is demonstrated in the case of formamidinium (FA) containing A 2 FA n−1 Pb n I 3n+1 formulations by employing (adamantan-1-yl)methanammonium (A) spacers exhibiting propensity for strong Van der Waals interactions complemented by structural adaptability. The molecular design translates into desirable structural features and phases with different compositions and dimensionalities, identified uniquely ...

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Section: Resultsmentioning

confidence: 99%

Section: Supramolecular Designmentioning

confidence: 99%

Supramolecular Engineering for Formamidinium‐Based Layered 2D Perovskite Solar Cells: Structural Complexity and Dynamics Revealed by Solid‐State NMR Spectroscopy

Milić

Kubicki

et al. 2019

Advanced Energy Materials

149

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“…In contrast, dynamical rotational environments in single crystals have been fabricated in molecular turnstiles, 25 molecular gyroscopes, [26][27][28][29] molecular gears, 30 and supramolecular rotators. [31][32][33][34][35][36][37] For instance, we have reported the supramolecular rotator structures of anilinium (Ani + ) and adamantylammonium (ADNH 3 + ) on the stator of [18]crown-6 and dibenzo[18]crown-6 (DB[18]crown-6) in monovalent [Ni(dmit) 2 ] À single crystals. [6][7][8]36,37 A molecular design to introduce the polarity change for molecular rotation has been attempted to show a ferroelectric supramolecular rotator, where the flip-flop motion of m-fluoroanilinium (m-FAni + ) on the DB[18]crown-6 stator realizes dipole inversion according to the flip-flop motion of polar F-groups in m-FAni + (DB[18]crown-6)[Ni(dmit) 2 ] À single crystals.…”

Section: Introductionmentioning

confidence: 99%

“…[31][32][33][34][35][36][37] For instance, we have reported the supramolecular rotator structures of anilinium (Ani + ) and adamantylammonium (ADNH 3 + ) on the stator of [18]crown-6 and dibenzo[18]crown-6 (DB[18]crown-6) in monovalent [Ni(dmit) 2 ] À single crystals. [6][7][8]36,37 A molecular design to introduce the polarity change for molecular rotation has been attempted to show a ferroelectric supramolecular rotator, where the flip-flop motion of m-fluoroanilinium (m-FAni + ) on the DB[18]crown-6 stator realizes dipole inversion according to the flip-flop motion of polar F-groups in m-FAni + (DB[18]crown-6)[Ni(dmit) 2 ] À single crystals. 38 Another type of interesting ferroelectric liquid crystalline material has been reported in alkylamide (-CONHC n H 2n+1 )substituted benzene derivatives, where the rotation of hydrogen-bonding polar alkylamide chains plays an essential role in ferroelectricity.…”

Section: Introductionmentioning

confidence: 99%

Simple molecular ferroelectrics:N,N′-dialkyl-terephthalamide derivatives in the solid phase

et al. 2022

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“…In particular, energy harvesting occurs during phase changes; thus, phase-transition materials may serve as energy-saving materials. Designing special inorganic-organic hybrid compounds with molecular dielectrics is an effective method for synthesizing ideal phase-transition materials [16][17][18][19].…”

Section: Introductionmentioning

confidence: 99%

Inorganic Anions Regulate the Phase Transition in Two Organic Cation Salts Containing [(4-Nitroanilinium)(18-crown-6)]+ Supramolecules

et al. 2017

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Two novel inorganic-organic hybrid supramolecular assemblies, namely, (4-HNA) (18-crown-6)(HSO 4 ) (1) and (4-HNA) 2 (18-crown-6) 2 (PF 6 ) 2 (CH 3 OH) (2) (4-HNA = 4-nitroanilinium), were synthesized and characterized by infrared spectroscopy, single X-ray diffraction, differential scanning calorimetry (DSC), and temperature-dependent dielectric measurements. The two compounds underwent reversible phase transitions at about 255 K and 265 K, respectively. These phase transitions were revealed and confirmed by the thermal anomalies in DSC measurements and abrupt dielectric anomalies during heating. The phase transition may have originated from the [(4-HNA)(18-crown-6)] + supramolecular cation. The inorganic anions tuned the crystal packings, and thus influenced the phase-transition points and types. The variable-temperature X-ray diffraction data for crystal 1 revealed the occurrence of a phase transition in the high-temperature phase with the space group of P2 1 /c and in the low-temperature phase with the space group of P2 1 /n. Crystal 2 exhibited the same space group P2 1 /c at different temperatures. The results indicated that crystals 1 and 2 both underwent an iso-structural phase transition.

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Supramolecular Rotor: Adamantylammonium([18]crown-6) in [Ni(dmit)₂]^- Salt

Cited by 44 publications

References 26 publications

Supramolecular Engineering for Formamidinium‐Based Layered 2D Perovskite Solar Cells: Structural Complexity and Dynamics Revealed by Solid‐State NMR Spectroscopy

Supramolecular Engineering for Formamidinium‐Based Layered 2D Perovskite Solar Cells: Structural Complexity and Dynamics Revealed by Solid‐State NMR Spectroscopy

Simple molecular ferroelectrics:N,N′-dialkyl-terephthalamide derivatives in the solid phase

Inorganic Anions Regulate the Phase Transition in Two Organic Cation Salts Containing [(4-Nitroanilinium)(18-crown-6)]+ Supramolecules

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Supramolecular Rotor: Adamantylammonium([18]crown-6) in [Ni(dmit)2]- Salt

Cited by 44 publications

References 26 publications

Supramolecular Engineering for Formamidinium‐Based Layered 2D Perovskite Solar Cells: Structural Complexity and Dynamics Revealed by Solid‐State NMR Spectroscopy

Supramolecular Engineering for Formamidinium‐Based Layered 2D Perovskite Solar Cells: Structural Complexity and Dynamics Revealed by Solid‐State NMR Spectroscopy

Simple molecular ferroelectrics:N,N′-dialkyl-terephthalamide derivatives in the solid phase

Inorganic Anions Regulate the Phase Transition in Two Organic Cation Salts Containing [(4-Nitroanilinium)(18-crown-6)]+ Supramolecules

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Product

Resources

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Supramolecular Rotor: Adamantylammonium([18]crown-6) in [Ni(dmit)₂]^- Salt