Construction and Charge-Transfer Complexation of Adamantane-Based Macrocycles and a Cage with Aromatic Ring Moieties

Adamantane-based macrocycles and a cage with aromatic ring moieties have been developed and structurally revealed by X-ray crystallographic analysis. The dimerized (1) and trimerized (2) macrocycles of binary molecules based on adamantane with acetylenic aromatic ring moieties were designed and effectively synthesized. Similarly, a cryptand-like macrobicyclic cage (3) was constructed from a trisubstituted adamantane derivative. Single-crystal X-ray analysis revealed that both cyclic compounds have nearly a rectangular shape with or without a solvent molecule in the cavity. The macrobicyclic cage has an inner space and accommodates a chloroform molecule via C−H···π interactions. Macrocycles and cage encapsulate 1,3,5-trinitrobenzene (4) as an electron-poor guest in a one-to-one complex via charge-transfer interactions in a parallel fashion, and showed the formation of molecular networks such as columns, tubes, 2D layers, and 3D networks composed of two different types through noncovalent interactions in the solid state

Construction and Charge-Transfer Complexation of Adamantane-Based Macrocycles and a Cage with Aromatic Ring Moieties

Adamantane-based macrocycles and a cage with aromatic ring moieties have been developed and structurally revealed by X-ray crystallographic analysis. The dimerized (1) and trimerized (2) macrocycles of binary molecules based on adamantane with acetylenic aromatic ring moieties were designed and effectively synthesized. Similarly, a cryptand-like macrobicyclic cage (3) was constructed from a trisubstituted adamantane derivative. Single-crystal X-ray analysis revealed that both cyclic compounds have nearly a rectangular shape with or without a solvent molecule in the cavity. The macrobicyclic cage has an inner space and accommodates a chloroform molecule via C−H···π interactions. Macrocycles and cage encapsulate 1,3,5-trinitrobenzene (4) as an electron-poor guest in a one-to-one complex via charge-transfer interactions in a parallel fashion, and showed the formation of molecular networks such as columns, tubes, 2D layers, and 3D networks composed of two different types through noncovalent interactions in the solid state

Hydrogen-Bonding Networks of Adamantane-Based Bisphenol Molecules: Toward the Preparation of Molecular Crystals with Channels

A series of adamantane-based bisphenol molecules with structurally related V-shaped skeletons were designed to examine the influence of molecular shapes and steric hindrances for the molecular association and packing of individual molecules in crystalline lattices. Single crystal X-ray analysis revealed that multiple intermolecular hydrogen bonds were formed between the hydroxyl groups of the phenol moieties. Crystallographic analysis of 1,3-bis(4-hydroxy-3,5-dimethylphenyl)adamantane (1) indicated the creation of a one-dimensional (1D) zigzag polymer through hydrogen bonds. In the crystals of 1,3-bis(3-bromo-4-hydroxyphenyl)adamantane (2), infinite 1D polymers composed of cyclic frameworks were sustained by intermolecular hydrogen bonds. 1,3-Bis(3-chloro-4-hydroxyphenyl)adamantane (3) and 1,3-bis(4-hydroxyphenyl)adamantane (4) formed frameworks with channels containing chloroform molecules in the solid state. Continuous 1D polymers consisting of cyclic frameworks were generated in crystals 3a and 4a, and these 1D polymers packed into two-dimensional (2D) layers with channel structures

Catalysis of Nucleobase via Multiple Hydrogen-Bonding Interactions: Acceleration of Aminolysis of 6-Chloropurine Derivatives by Uracils

Catalysis of Nucleobase via Multiple Hydrogen-Bonding Interactions:  Acceleration of Aminolysis of 6-Chloropurine Derivatives by Uracil

Pseudopolymorph and Charge-Transfer Co-Crystal of Disubstituted Adamantane containing Dimethoxyphenol Moieties

A disubstituted adamantane containing dimethoxyphenol moieties was synthesized by an acid-condensation reaction. The disubstituted adamantane is a new building block, designed particularly for the rational construction of supramolecular structures that are capable of encapsulating and aligning guest molecules, leading to the formation of extended polymeric networks. Single crystal X-ray analysis revealed that the binary molecule based on adamantane has three types of crystal forms, 1a, 1b, and 1c, containing no additional molecule, water and benzene, and 1,3,5-trinitrobenzene, respectively. In crystal 1a, each hydroxyl group of dimethoxyphenol moieties participates in two intermolecular hydrogen bonds as both donor and acceptor, producing infinite one-dimensional (1D) zigzag chains. Individual chains assemble into a two-dimensional (2D) layered structure via C−H···O interactions between protons of adamantane and oxygen atoms of methoxy groups. Crystal 1b, which is pseudopolymorph of crystal 1a, has a cyclic network consisting of two molecules of disubstituted adamantane and two molecules of water, generated by hydrogen bonds, a benzene molecule accommodated in the cavity. This stacks into a tubular structure via water molecules, which again align into a 2D layered structure through water molecules. Crystal 1c shows a discrete cyclic network accomplished through hydrogen bonds between two molecules of disubstituted adamantane and two molecules of 1,3,5-trinitrobenzene. The finite cyclic network stacks to form 1D columnar aggregates due to van der Waals interactions among the adamantyl groups, resulting in the formation of a channel structure. Individual columns are intermolecularly interdigitated via donor−acceptor interactions between the dimethoxyphenol moieties and 1,3,5-trinitrobenzene, resulting in the formation of a 2D layered structure. The three types of crystals are produced by multiple hydrogen bonding, C−H···O, and donor−acceptor interactions

Hydrogen-Bonding Networks of Adamantane-Based Bisphenol Molecules: Toward the Preparation of Molecular Crystals with Channels

A series of adamantane-based bisphenol molecules with structurally related V-shaped skeletons were designed to examine the influence of molecular shapes and steric hindrances for the molecular association and packing of individual molecules in crystalline lattices. Single crystal X-ray analysis revealed that multiple intermolecular hydrogen bonds were formed between the hydroxyl groups of the phenol moieties. Crystallographic analysis of 1,3-bis(4-hydroxy-3,5-dimethylphenyl)adamantane (1) indicated the creation of a one-dimensional (1D) zigzag polymer through hydrogen bonds. In the crystals of 1,3-bis(3-bromo-4-hydroxyphenyl)adamantane (2), infinite 1D polymers composed of cyclic frameworks were sustained by intermolecular hydrogen bonds. 1,3-Bis(3-chloro-4-hydroxyphenyl)adamantane (3) and 1,3-bis(4-hydroxyphenyl)adamantane (4) formed frameworks with channels containing chloroform molecules in the solid state. Continuous 1D polymers consisting of cyclic frameworks were generated in crystals 3a and 4a, and these 1D polymers packed into two-dimensional (2D) layers with channel structures

Hydrogen-Bonding Networks of Adamantane-Based Bisphenol Molecules: Toward the Preparation of Molecular Crystals with Channels

A series of adamantane-based bisphenol molecules with structurally related V-shaped skeletons were designed to examine the influence of molecular shapes and steric hindrances for the molecular association and packing of individual molecules in crystalline lattices. Single crystal X-ray analysis revealed that multiple intermolecular hydrogen bonds were formed between the hydroxyl groups of the phenol moieties. Crystallographic analysis of 1,3-bis(4-hydroxy-3,5-dimethylphenyl)adamantane (1) indicated the creation of a one-dimensional (1D) zigzag polymer through hydrogen bonds. In the crystals of 1,3-bis(3-bromo-4-hydroxyphenyl)adamantane (2), infinite 1D polymers composed of cyclic frameworks were sustained by intermolecular hydrogen bonds. 1,3-Bis(3-chloro-4-hydroxyphenyl)adamantane (3) and 1,3-bis(4-hydroxyphenyl)adamantane (4) formed frameworks with channels containing chloroform molecules in the solid state. Continuous 1D polymers consisting of cyclic frameworks were generated in crystals 3a and 4a, and these 1D polymers packed into two-dimensional (2D) layers with channel structures

Construction and Charge-Transfer Complexation of Adamantane-Based Macrocycles and a Cage with Aromatic Ring Moieties

Adamantane-based macrocycles and a cage with aromatic ring moieties have been developed and structurally revealed by X-ray crystallographic analysis. The dimerized (1) and trimerized (2) macrocycles of binary molecules based on adamantane with acetylenic aromatic ring moieties were designed and effectively synthesized. Similarly, a cryptand-like macrobicyclic cage (3) was constructed from a trisubstituted adamantane derivative. Single-crystal X-ray analysis revealed that both cyclic compounds have nearly a rectangular shape with or without a solvent molecule in the cavity. The macrobicyclic cage has an inner space and accommodates a chloroform molecule via C−H···π interactions. Macrocycles and cage encapsulate 1,3,5-trinitrobenzene (4) as an electron-poor guest in a one-to-one complex via charge-transfer interactions in a parallel fashion, and showed the formation of molecular networks such as columns, tubes, 2D layers, and 3D networks composed of two different types through noncovalent interactions in the solid state

Construction and Charge-Transfer Complexation of Adamantane-Based Macrocycles and a Cage with Aromatic Ring Moieties

Adamantane-based macrocycles and a cage with aromatic ring moieties have been developed and structurally revealed by X-ray crystallographic analysis. The dimerized (1) and trimerized (2) macrocycles of binary molecules based on adamantane with acetylenic aromatic ring moieties were designed and effectively synthesized. Similarly, a cryptand-like macrobicyclic cage (3) was constructed from a trisubstituted adamantane derivative. Single-crystal X-ray analysis revealed that both cyclic compounds have nearly a rectangular shape with or without a solvent molecule in the cavity. The macrobicyclic cage has an inner space and accommodates a chloroform molecule via C−H···π interactions. Macrocycles and cage encapsulate 1,3,5-trinitrobenzene (4) as an electron-poor guest in a one-to-one complex via charge-transfer interactions in a parallel fashion, and showed the formation of molecular networks such as columns, tubes, 2D layers, and 3D networks composed of two different types through noncovalent interactions in the solid state

Hydrogen-Bonding Networks of Adamantane-Based Bisphenol Molecules: Toward the Preparation of Molecular Crystals with Channels

A series of adamantane-based bisphenol molecules with structurally related V-shaped skeletons were designed to examine the influence of molecular shapes and steric hindrances for the molecular association and packing of individual molecules in crystalline lattices. Single crystal X-ray analysis revealed that multiple intermolecular hydrogen bonds were formed between the hydroxyl groups of the phenol moieties. Crystallographic analysis of 1,3-bis(4-hydroxy-3,5-dimethylphenyl)adamantane (1) indicated the creation of a one-dimensional (1D) zigzag polymer through hydrogen bonds. In the crystals of 1,3-bis(3-bromo-4-hydroxyphenyl)adamantane (2), infinite 1D polymers composed of cyclic frameworks were sustained by intermolecular hydrogen bonds. 1,3-Bis(3-chloro-4-hydroxyphenyl)adamantane (3) and 1,3-bis(4-hydroxyphenyl)adamantane (4) formed frameworks with channels containing chloroform molecules in the solid state. Continuous 1D polymers consisting of cyclic frameworks were generated in crystals 3a and 4a, and these 1D polymers packed into two-dimensional (2D) layers with channel structures