Theoretical Studies on Pd(II)-Catalyzed <i>meta</i>-Selective C–H Bond Arylation of Arenes

Direct C–H arylation of arene is often the most efficient way to construct a biaryl product. However, <i>meta</i>-selective C–H arylation is much less reported than <i>ortho</i> selectivity. In this work, DFT studies have been performed to systematically investigate the factors that may affect the competition between <i>meta</i> and <i>ortho</i> selectivity. Our results suggest that a weak directing group is essential to suppress the commonly observed CMD on <i>ortho</i> position, so that the <i>meta</i> position can be activated by a migratory insertion pathway. In addition, we find that naphthyl substrates are more likely to undergo a migratory insertion due to its significantly lower dearomatization energy, and a more oxidizing metal can promote the migratory insertion pathway by lowering the succeeding reductive deprotonation

Theoretical Studies on Pd(II)-Catalyzed <i>meta</i>-Selective C–H Bond Arylation of Arenes

Direct C–H arylation of arene is often the most efficient way to construct a biaryl product. However, <i>meta</i>-selective C–H arylation is much less reported than <i>ortho</i> selectivity. In this work, DFT studies have been performed to systematically investigate the factors that may affect the competition between <i>meta</i> and <i>ortho</i> selectivity. Our results suggest that a weak directing group is essential to suppress the commonly observed CMD on <i>ortho</i> position, so that the <i>meta</i> position can be activated by a migratory insertion pathway. In addition, we find that naphthyl substrates are more likely to undergo a migratory insertion due to its significantly lower dearomatization energy, and a more oxidizing metal can promote the migratory insertion pathway by lowering the succeeding reductive deprotonation

An [Au₁₃]⁵⁺ Approach to the Study of Gold Nanoclusters

Recently, many examples of gold nanoclusters have been synthesized due to their exceptional spectroscopic properties and potential applications in nanotechnology. In this work we put forward an approach based on the icosahedral [Au₁₃]⁵⁺ unit and summarize three possible extensions of the unit: wrapping, bonding, and vertex sharing. We show that the electronic structure of such clusters can be treated in a more localized manner and show how the approach could be applied to understand the structure and bonding of a large variety of gold nanoclusters

Achieving <i>In Situ</i> Dynamic Fluorescence in the Solid State through Synergizing Cavities of Macrocycle and Channels of Framework

To achieve in situ dynamic fluorescence in the solid state and unveil the mechanism remain a formidable challenge. Herein, through synergizing the cavities of macrocycles for dynamic complexing and the channels of frameworks for facile transit, we construct intrinsic channels from an emissive cyclophane and realize precisely tunable emission in the solid state through the sequential guests’ exchange. Specifically, two design criteria involve (1) The twisted cyanostilbene units not only endow the systems with solid-state fluorescence but also tailor the π–π interactions in the complex to generate the desired emission and (2) the large cavity of cyclophane results in the formation of ternary complexes with controllable binding affinity which further assemble into robust channels for the guests’ exchange in the bulky state. This strategy unifies the advantages of both macrocycle and framework in one system, achieving visualization, recyclability, and easy processability simultaneously. The present study paves an easy, efficient, and general platform for constructing dynamic optical materials

Achieving <i>In Situ</i> Dynamic Fluorescence in the Solid State through Synergizing Cavities of Macrocycle and Channels of Framework

To achieve in situ dynamic fluorescence in the solid state and unveil the mechanism remain a formidable challenge. Herein, through synergizing the cavities of macrocycles for dynamic complexing and the channels of frameworks for facile transit, we construct intrinsic channels from an emissive cyclophane and realize precisely tunable emission in the solid state through the sequential guests’ exchange. Specifically, two design criteria involve (1) The twisted cyanostilbene units not only endow the systems with solid-state fluorescence but also tailor the π–π interactions in the complex to generate the desired emission and (2) the large cavity of cyclophane results in the formation of ternary complexes with controllable binding affinity which further assemble into robust channels for the guests’ exchange in the bulky state. This strategy unifies the advantages of both macrocycle and framework in one system, achieving visualization, recyclability, and easy processability simultaneously. The present study paves an easy, efficient, and general platform for constructing dynamic optical materials

Achieving <i>In Situ</i> Dynamic Fluorescence in the Solid State through Synergizing Cavities of Macrocycle and Channels of Framework

To achieve in situ dynamic fluorescence in the solid state and unveil the mechanism remain a formidable challenge. Herein, through synergizing the cavities of macrocycles for dynamic complexing and the channels of frameworks for facile transit, we construct intrinsic channels from an emissive cyclophane and realize precisely tunable emission in the solid state through the sequential guests’ exchange. Specifically, two design criteria involve (1) The twisted cyanostilbene units not only endow the systems with solid-state fluorescence but also tailor the π–π interactions in the complex to generate the desired emission and (2) the large cavity of cyclophane results in the formation of ternary complexes with controllable binding affinity which further assemble into robust channels for the guests’ exchange in the bulky state. This strategy unifies the advantages of both macrocycle and framework in one system, achieving visualization, recyclability, and easy processability simultaneously. The present study paves an easy, efficient, and general platform for constructing dynamic optical materials

Achieving <i>In Situ</i> Dynamic Fluorescence in the Solid State through Synergizing Cavities of Macrocycle and Channels of Framework

To achieve in situ dynamic fluorescence in the solid state and unveil the mechanism remain a formidable challenge. Herein, through synergizing the cavities of macrocycles for dynamic complexing and the channels of frameworks for facile transit, we construct intrinsic channels from an emissive cyclophane and realize precisely tunable emission in the solid state through the sequential guests’ exchange. Specifically, two design criteria involve (1) The twisted cyanostilbene units not only endow the systems with solid-state fluorescence but also tailor the π–π interactions in the complex to generate the desired emission and (2) the large cavity of cyclophane results in the formation of ternary complexes with controllable binding affinity which further assemble into robust channels for the guests’ exchange in the bulky state. This strategy unifies the advantages of both macrocycle and framework in one system, achieving visualization, recyclability, and easy processability simultaneously. The present study paves an easy, efficient, and general platform for constructing dynamic optical materials

Achieving <i>In Situ</i> Dynamic Fluorescence in the Solid State through Synergizing Cavities of Macrocycle and Channels of Framework

To achieve in situ dynamic fluorescence in the solid state and unveil the mechanism remain a formidable challenge. Herein, through synergizing the cavities of macrocycles for dynamic complexing and the channels of frameworks for facile transit, we construct intrinsic channels from an emissive cyclophane and realize precisely tunable emission in the solid state through the sequential guests’ exchange. Specifically, two design criteria involve (1) The twisted cyanostilbene units not only endow the systems with solid-state fluorescence but also tailor the π–π interactions in the complex to generate the desired emission and (2) the large cavity of cyclophane results in the formation of ternary complexes with controllable binding affinity which further assemble into robust channels for the guests’ exchange in the bulky state. This strategy unifies the advantages of both macrocycle and framework in one system, achieving visualization, recyclability, and easy processability simultaneously. The present study paves an easy, efficient, and general platform for constructing dynamic optical materials

Achieving <i>In Situ</i> Dynamic Fluorescence in the Solid State through Synergizing Cavities of Macrocycle and Channels of Framework

To achieve in situ dynamic fluorescence in the solid state and unveil the mechanism remain a formidable challenge. Herein, through synergizing the cavities of macrocycles for dynamic complexing and the channels of frameworks for facile transit, we construct intrinsic channels from an emissive cyclophane and realize precisely tunable emission in the solid state through the sequential guests’ exchange. Specifically, two design criteria involve (1) The twisted cyanostilbene units not only endow the systems with solid-state fluorescence but also tailor the π–π interactions in the complex to generate the desired emission and (2) the large cavity of cyclophane results in the formation of ternary complexes with controllable binding affinity which further assemble into robust channels for the guests’ exchange in the bulky state. This strategy unifies the advantages of both macrocycle and framework in one system, achieving visualization, recyclability, and easy processability simultaneously. The present study paves an easy, efficient, and general platform for constructing dynamic optical materials

Achieving <i>In Situ</i> Dynamic Fluorescence in the Solid State through Synergizing Cavities of Macrocycle and Channels of Framework

To achieve in situ dynamic fluorescence in the solid state and unveil the mechanism remain a formidable challenge. Herein, through synergizing the cavities of macrocycles for dynamic complexing and the channels of frameworks for facile transit, we construct intrinsic channels from an emissive cyclophane and realize precisely tunable emission in the solid state through the sequential guests’ exchange. Specifically, two design criteria involve (1) The twisted cyanostilbene units not only endow the systems with solid-state fluorescence but also tailor the π–π interactions in the complex to generate the desired emission and (2) the large cavity of cyclophane results in the formation of ternary complexes with controllable binding affinity which further assemble into robust channels for the guests’ exchange in the bulky state. This strategy unifies the advantages of both macrocycle and framework in one system, achieving visualization, recyclability, and easy processability simultaneously. The present study paves an easy, efficient, and general platform for constructing dynamic optical materials