Multicomponent Organic Alloys Based on Organic Layered Crystals

Sada, Kazuki; Inoue, Koichiro; Tanaka, Tomoyuki; Epergyes, Attila; Tohnai, Norimitsu; Miyata, Mikiji

doi:10.1002/ange.200501678

Cited by 22 publications

(5 citation statements)

References 70 publications

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“…Creating multicomponent solid solutions of organic molecules, however, is challenging because these molecules possess intricate shapes and participate in directional intermolecular interactions 3. Not surprisingly, most molecule‐based solid solutions contain only two components 7. We describe a supramolecular approach for the preparation of solid solutions that contain three or more organic molecules.…”

Section: Methodsmentioning

confidence: 99%

A Supramolecular Approach to Organic Alloys: Cocrystals and Three‐ and Four‐Component Solid Solutions of 1,4‐Diazabicyclo[2.2.2]octane and 4‐X‐Phenols (X=Cl, CH₃, Br)

2007

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Herein, we describe the preparation of binary cocrystals and ternary and quaternary solid solutions of 1,4-diazabicyclo-[2.2.2]octane (DABCO) and 4-X-phenols (X = Cl, CH 3 , Br). Multicomponent solids, be they cocrystals or solid solutions, are materials that may exhibit new or superior functionalities relative to the individual components.[1] Though molecular complexes have been studied for a long time, [1][2][3] the design of cocrystals containing more than two different components remains a challenging task.[4] Except for a few notable contributions, [5] most studies on organic cocrystals led only to the formation of binary organic solids.[1] In contrast, metals and inorganic compounds readily form multicomponent solids in the form of solid solutions.[6] Creating multicomponent solid solutions of organic molecules, however, is challenging because these molecules possess intricate shapes and participate in directional intermolecular interactions. [3] Not surprisingly, most molecule-based solid solutions contain only two components. [7] We describe a supramolecular approach for the preparation of solid solutions that contain three or more organic molecules. The principal advantage of solid solutions is that their properties can be modulated by the gradual modification of the relative ratio of the components.[8]Scheme 1 shows our approach to the formation of organic alloys. We begin with a trimolecular motif wherein a central molecule (A) is connected to two peripheral molecules (B or C) through similar intermolecular interactions. If the two peripheral molecules are identical, the binary cocrystals AB 2 or AC 2 are formed. If they are different, a ternary cocrystal BAC or a ternary solid solution A(B n C 1Àn ) 2 (0 < n < 1) can be formed, depending on the similarity of the sizes and shapes of the peripheral molecules. Adding another isosteric component (D) can lead to a quaternary solid solution A(B n C m D p ) 2 (n + m + p = 1, 0 < n, m, p < 1).We use DABCO as the central molecule and 4-X-phenols (X = Cl, CH 3 , Br) as the peripheral molecules (Scheme 2). The chloro, methyl, and bromo substituents of the 4-Xphenols have similar shapes and comparable sizes (20, 24, and 28 3 ), [9] and do not interfere with the O À H···N hydrogen bonding required for the trimolecular assembly. We surmised that the size, shape, and chemical similarity of the 4-Xphenols would enable the formation of solid solutions upon crystallization of DABCO with two or three of the phenols. We call these crystalline materials supramolecular solid solutions because their repeat unit is a trimolecular assembly.[10]Single crystals of binary cocrystals and of ternary and quaternary solid solutions (having equimolar ratios of phenols) suitable for X-ray diffraction were grown from benzene solutions (Table 1; Scheme 2).[11] The binary cocrystals ClCl and MeMe are isostructural; [12] Figure 1 a shows the structure of ClCl. The unit cell of MeMe is larger than that of ClCl, in accordance with the larger size of the methyl groups relative to the chlo...

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Section: Methodsmentioning

confidence: 99%

A Supramolecular Approach to Organic Alloys: Cocrystals and Three‐ and Four‐Component Solid Solutions of 1,4‐Diazabicyclo[2.2.2]octane and 4‐X‐Phenols (X=Cl, CH₃, Br)

2007

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“…2 However for organic molecular crystals, with diverse structures governed by weak intermolecular forces, such exchanges are more problematic. There are some examples where solid solutions (“organic alloys”)3 are formed from molecules which can be mixed in any ratio within the same crystal structure. However, this has only been possible where the molecules concerned are very similar in size, shape, and nature 1.…”

Section: Organic Alloys Formed From Steroidal Ureas 1 Andmentioning

confidence: 99%

“…However, this has only been possible where the molecules concerned are very similar in size, shape, and nature 1. 3, 4 Herein we report a new approach to the preparation of crystals from continuously variable mixtures of organic molecules. The strategy allows the incorporation of multiple and diverse units, including molecules which may not crystallize by themselves.…”

Section: Organic Alloys Formed From Steroidal Ureas 1 Andmentioning

confidence: 99%

Nanoporous Organic Alloys

et al. 2011

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Kristall‐Tuning: Organische Moleküle können bevorzugt mit Molekülen der eigenen Sorte kristallisieren, was eine Feinabstimmung der Kristalleigenschaften durch Dotierung oder Vermischung verhindert. Nanoporöse Steroide (siehe Bild) bilden eine Ausnahme, weil sie in ihren Kanälen verschiedene Endgruppen (angedeutet durch Sechsecke und Kugeln) beherbergen können. Sie können in beliebigem Verhältnis cokristallisiert werden und liefern eine breite Spanne von chiralen, potenziell porösen kristallinen Materialien.

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“…Solid solutions are defined as multicomponent crystalline systems in which the concentrations of two or more components occupying the same lattice position can be continuously varied between two compositional limits (see Figure a). Solid solutions are challenging to discover in molecular materials because functional groups responsible for modifying the electronic properties of a molecule tend to exhibit unique interaction modes in the solid state . As a result of this interaction selectivity, introduction of additional components often results in a physical mixture of multiple solid phases or the emergence of a new packing motif upon stoichiometric inclusion of the desired compound.…”

mentioning

confidence: 99%

Quaternary Charge-Transfer Solid Solutions: Electronic Tunability through Stoichiometry

2019

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Charge-transfer (CT) cocrystals formed between π-electron donor and acceptor molecules present diverse electronic behavior that can be rapidly modified due to the exchangeable nature of the CT partners. Unfortunately, chemical modifications to the donor and/or acceptor molecules often result in altered crystal packing that yields unpredictable changes in charge transfer and electronic coupling. Formation of solid solutions between isomorphous CT cocrystals offers an approach to predictably tune the electronic performance of CT materials because the packing motif is unaffected by compositional changes. We have formed ternary and quaternary CT solid solutions containing 4,6-dimethyldibenzothiophene (DMDBT), 4,6-dimethyldibenzoselenophene (DMDBS), 2,3-dichloro-5,6-dicyanobenzoquinone (DDQ), and 2,3-dibromo-5,6-dicyanobenzoquinone (DBQ) and have mapped the composition-dependent stability field for these materials using a combination of single-crystal X-ray diffraction, energy dispersive X-ray spectroscopy, and Raman spectroscopy. The CT solid solutions show tunable degrees of charge transfer (ρ), ranging from 0.005 to 0.19 e, and optical band gaps (E opt) between 1.26(1) and 1.38(1) eV that are dependent on the DDQ:DBQ molar ratio. Additionally, we have exploited the isostructurality of the DMDBT–DDQ and DMDBT–DBQ cocrystal phases to produce single crystals with core–shell structures, demonstrating that methods adopted to optimize and passivate inorganic electronic materials can also be implemented for organics.

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Multicomponent Organic Alloys Based on Organic Layered Crystals

Cited by 22 publications

References 70 publications

A Supramolecular Approach to Organic Alloys: Cocrystals and Three‐ and Four‐Component Solid Solutions of 1,4‐Diazabicyclo[2.2.2]octane and 4‐X‐Phenols (X=Cl, CH₃, Br)

A Supramolecular Approach to Organic Alloys: Cocrystals and Three‐ and Four‐Component Solid Solutions of 1,4‐Diazabicyclo[2.2.2]octane and 4‐X‐Phenols (X=Cl, CH₃, Br)

Nanoporous Organic Alloys

Quaternary Charge-Transfer Solid Solutions: Electronic Tunability through Stoichiometry

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Multicomponent Organic Alloys Based on Organic Layered Crystals

Cited by 22 publications

References 70 publications

A Supramolecular Approach to Organic Alloys: Cocrystals and Three‐ and Four‐Component Solid Solutions of 1,4‐Diazabicyclo[2.2.2]octane and 4‐X‐Phenols (X=Cl, CH3, Br)

A Supramolecular Approach to Organic Alloys: Cocrystals and Three‐ and Four‐Component Solid Solutions of 1,4‐Diazabicyclo[2.2.2]octane and 4‐X‐Phenols (X=Cl, CH3, Br)

Nanoporous Organic Alloys

Quaternary Charge-Transfer Solid Solutions: Electronic Tunability through Stoichiometry

Contact Info

Product

Resources

About

A Supramolecular Approach to Organic Alloys: Cocrystals and Three‐ and Four‐Component Solid Solutions of 1,4‐Diazabicyclo[2.2.2]octane and 4‐X‐Phenols (X=Cl, CH₃, Br)

A Supramolecular Approach to Organic Alloys: Cocrystals and Three‐ and Four‐Component Solid Solutions of 1,4‐Diazabicyclo[2.2.2]octane and 4‐X‐Phenols (X=Cl, CH₃, Br)