Growth of Nanocrystals in a Single Crystal of Different Materials: A Way of Giving Function to Molecular Crystals

Naito, T.; Kakizaki, Akihiro; Inabe, Tamotsu; Sakai, Ryosuke; Nishibori, Eiji; Sawa, Hiroshi

doi:10.1021/cg101295p

Cited by 9 publications

(12 citation statements)

References 19 publications

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“…However, annealing above ³373 K suddenly and markedly accelerated and completed the decomposition of Ag(DCl) 2 to AgCl. 120 These observations agreed with the temperaturedependent powder XRD-DSC as well as XPS measured on the pressed powder pellets of AgCl, the pristine and the irradiated Ag(DCl) 2 . 120 Thus it is concluded that AgCl are nanocrystals produced in the photochemical decomposition of Ag(DCl) 2 and that all of the nanocrystals are highly oriented as if they belong to a single crystal.…”

supporting

confidence: 84%

“…Although the conduction properties of the matrix and the nanocrystals were inversed between nanoAgX@Ag(DX) 2 and commercially available varistors, the former also exhibited varistor-like behavior or diode-like behavior ( Figure 34). 120 In conclusion, without using any mask, the optical doping can realize a similar function to varistors and diodes simply by irradiating the single crystals of Ag(DX) 2 . …”

mentioning

confidence: 93%

“…Compared with isolated AgCl crystals, the AgCl nanocrystals decreased the melting point and the lattice constants by ³80 K and 0.01 ¡, respectively. 120 The differences suggest that the original Ag(DCl) 2 lattice served as a template in the crystal growth of AgCl, and accordingly that the two kinds of lattices, i.e., those of Ag(DCl) 2 and AgCl interact with each other. If the interaction lowers their total energy, the mixed crystal retains their interface as large an area as possible for closest interaction during the decomposition.…”

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confidence: 99%

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Development of a Control Method for Conduction and Magnetism in Molecular Crystals

Naito

2016

Bulletin of the Chemical Society of Japan

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This study concerns development of a non-destructive method to control conduction and magnetism of molecular solids such as single crystals of charge-transfer complexes. The method is named “optical doping”, where appropriate irradiation is utilized under ambient conditions. Owing to this feature, it can be applied to a wide range of substances while measuring the properties during the control. In addition, the method adds unique conduction and magnetic properties to common insulators. Unlike other doping methods, optical doping only affects the properties and/or structures of the irradiated part of a sample while leaving the rest of the sample unchanged. There are two patterns in the optical doping. Irreversible optical doping produces junction-structures on the single molecular crystals, which exhibit characteristic behavior of semiconductor devices such as diodes and varistors. Reversible optical doping produces “giant photoconductors” and “photomagnetic conductors” by realizing unprecedented metallic photoconduction. In the latter case, localized spins are also excited to produce a Kondo system, where carriers and localized spins interact with each other. Not only the control of conduction and magnetism, the optical doping has realized the observation of physical properties in molecular crystals hardly observed under any thermodynamic condition.

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confidence: 84%

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confidence: 93%

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confidence: 99%

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Development of a Control Method for Conduction and Magnetism in Molecular Crystals

Naito

2016

Bulletin of the Chemical Society of Japan

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“…63,147 Generally, lower band gaps are necessary to support electrical conductivity (although it is not the sole factor required for achieving high electrical conductivities). 63 When the CGCNN model is used to predict the band gaps of all 42,349 structures that compose the QMOF-42349 dataset, one of the lowest band gap materials is predicted to be Ag(DCl) 2 (DCl = 2,5-Cl,Cl-N,N 0 -dicyanoquinone diamine) (refcode: OTARUX), 154 which is known from experiments to exhibit metallic character via organic radicals that connect the Ag(I) cations. 154 The introduction of radical or redox-active linking units is a well-established strategy to increase the electrical conductivity of framework materials.…”

Section: Highlighting Notable Low Band Gap Mofsmentioning

confidence: 99%

Machine learning the quantum-chemical properties of metal–organic frameworks for accelerated materials discovery

Rosen

Iyer

Ray

et al. 2021

Matter

277

259

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Using a new database of electronic structure properties derived from highthroughput density functional theory calculations for thousands of metal-organic frameworks (MOFs), we benchmark a variety of machine learning models to accurately and rapidly predict MOF band gaps. Unsupervised dimensionality reduction techniques are also used to map the MOF feature space and identify otherwise subtle structure-property relationships. We anticipate that machine learning models derived from this new database will accelerate the discovery of promising MOFs with targeted quantum-chemical properties.

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“…Paying attention to such unique features of molecular crystals, the control of conduction [19,20], or magnetism [21,22], or other physical properties [23][24][25][26][27][28] was carried out using photochemical redox reactions in solid states. In the reactions, photo-induced electron transfer occurs between two different kinds of molecular species in the crystal, e.g., the cations and the anions; one species is responsible for conduction and/or magnetism, and the other serves as the charge reservoir in high-T C cuprates [29].…”

Section: Introductionmentioning

confidence: 99%

Direct Control of Spin Distribution and Anisotropy in Cu-Dithiolene Complex Anions by Light

2016

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Electrical and magnetic properties are dominated by the (de)localization and the anisotropy in the distribution of unpaired electrons in solids. In molecular materials, these properties have been indirectly controlled through crystal structures using various chemical modifications to affect molecular structures and arrangements. In the molecular crystals, since the energy band structures can be semi-quantitatively known using band calculations and solid state spectra, one can anticipate the (de)localization of unpaired electrons in particular bands/levels, as well as interactions with other electrons. Thus, direct control of anisotropy and localization of unpaired electrons by locating them in selected energy bands/levels would realize more efficient control of electrical and magnetic properties. In this work, it has been found that the unpaired electrons on Cu(II)-complex anions can be optically controlled to behave as anisotropically-delocalized electrons (under dark) or isotropically-localized electrons like free electrons (under UV), the latter of which has hardly been observed in the ground states of Cu(II)-complexes by any chemical modifications. Although the compounds examined in this work did not switch between conductors and magnets, these findings indicate that optical excitation in the [Cu(dmit) 2 ] 2´s alts should be an effective method to control spin distribution and anisotropy.

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Growth of Nanocrystals in a Single Crystal of Different Materials: A Way of Giving Function to Molecular Crystals

Cited by 9 publications

References 19 publications

Development of a Control Method for Conduction and Magnetism in Molecular Crystals

Development of a Control Method for Conduction and Magnetism in Molecular Crystals

Machine learning the quantum-chemical properties of metal–organic frameworks for accelerated materials discovery

Direct Control of Spin Distribution and Anisotropy in Cu-Dithiolene Complex Anions by Light

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