本文以水溶性柱[6]芳烃(P[6]A)作为主体分子,萘基苯基丙烯腈衍生物(NPA)作为客体分子,两者在水中通过主–客体相互作用形成两亲性复合物,并进一步自组装成纳米颗粒(P[6]A-NPA)。该纳米颗粒可以对荧光染料尼罗红(NiR)进行包载,成功构筑...本文以水溶性柱[6]芳烃(P[6]A)作为主体分子,萘基苯基丙烯腈衍生物(NPA)作为客体分子,两者在水中通过主–客体相互作用形成两亲性复合物,并进一步自组装成纳米颗粒(P[6]A-NPA)。该纳米颗粒可以对荧光染料尼罗红(NiR)进行包载,成功构筑了一种新型水相人工光捕获体系(P[6]A-NPA-NiR)。值得注意的是,当P[6]A-NPA与NiR的摩尔比达到100:1时,该体系的能量转移效率和天线效应分别达到了55%和14.0,为水相超分子人工光捕获领域的研究提供了新思路。A water-soluble pillar[6]arene (P[6]A) was used as host molecule and a naphthalenyl-phenyl-acrylonitrile-based derivative (NPA) was used as guest molecule. The amphiphilic complex of P[6]A-NPA was formed through host-guest interactions in water and further self-assembled into P[6]A-NPA nanoparticles. Moreover, the above nanoparticles can encapsulate the fluorescent dye Nile Red (NiR) and construct a novel aqueous artificial light-harvesting system (P[6]A-NPA-NiR). Notably, when the molar ratio of NPA and NiR reaches 100:1, the energy transfer efficiency and antenna effect of the system reach 55% and 14.0, providing new ideas in the field of aqueous supramolecular artificial light-harvesting systems.展开更多
本文设计合成了一种具有聚集诱导效应的苯基吡啶基丙烯腈衍生物(PPAD)作为客体分子,通过与羧酸盐修饰的水溶性柱[5]芳烃(P[5]A)进行主–客体作用,在水中形成了超分子两亲体,并自组装成P[5]A-PPAD超分子纳米颗粒。由于P[5]A-PPAD具有明...本文设计合成了一种具有聚集诱导效应的苯基吡啶基丙烯腈衍生物(PPAD)作为客体分子,通过与羧酸盐修饰的水溶性柱[5]芳烃(P[5]A)进行主–客体作用,在水中形成了超分子两亲体,并自组装成P[5]A-PPAD超分子纳米颗粒。由于P[5]A-PPAD具有明显的荧光发射能力,可将其作为能量供体,并对能量受体荧光染料4,7-二(2-噻吩基)-2,1,3-苯并噻二唑(DBT)进行包载,成功构筑了一种新型P[5]A-PPAD-DBT超分子人工光捕获体系。通过性能测试发现,P[5]A-PPAD-DBT体系的能量转移效率为52.7%,天线效应为11.6,具有良好的水相人工光捕获能力,为水相人工光捕获体系的构筑与发展提供了新的思路。In this work, a phenylpyridinylacrylonitrile-based derivative (PPAD) with aggregation inducing effect was initially designed and synthesized, which was used as a guest molecule. Through host-guest interaction with a water-soluble pillar[5]arene (P[5]A) modified with carboxylate salts, P[5]A-PPAD supramolecular amphiphilics were formed in water and self-assembled into P[5]A-PPAD supramolecular nanoparticles. Due to the significant fluorescence emission ability of P[5]A-PPAD, P[5]A-PPAD could be used as an energy donor and encapsulate the energy acceptor fluorescent dye 4,7-di(2-thienyl)-2,1,3-benzothiadiazole (DBT) to construct P[5]A-PPAD-DBT supramolecular artificial light harvesting system. After further investigation of light-harvesting performance, the energy transfer efficiency of P[5]A-PPAD-DBT system was 52.7%, and the antenna effect was 11.6, which indicated a good aqueous light-harvesting ability, providing new ideas for the construction and development of supramolecular artificial light harvesting systems.展开更多
Molecular catalysts for H2-evolution are of interest for their integration into light-harvesting complexes for photocatalytic water splitting.Here,we report the meso-tetra(4-carboxyphenyl)porphine[(TCPP)Pt^(Ⅱ)]comple...Molecular catalysts for H2-evolution are of interest for their integration into light-harvesting complexes for photocatalytic water splitting.Here,we report the meso-tetra(4-carboxyphenyl)porphine[(TCPP)Pt^(Ⅱ)]complex as a molecular H2-evolving photocatalyst using chloranilic acid(CA)as a sacrificial electron donor,the choice of which is critical to the stability of the photocatalyst.When triethanolamine was used,[(TCPP)Pt^(Ⅱ)]decomposed to form Pt nanoparticles.Density functional theory calculations together with evidence from electrochemical and spectroscopic analyses suggested that the catalysis was possibly initiated by a proton-coupled electron transfer(PCET)to form[(TCPP)Pt^(Ⅰ)]-N-H,followed by another electron injection and protonation to form a[(TCPP)Pt^(Ⅱ)-hydride]-N-H intermediate that can release H2.As the whole catalytic cycle involves the injection of multiple electrons,a light-harvesting network should be helpful by providing multiple photo-induced electrons.Thus,we integrated this molecular catalyst into a light-harvesting metal-organic framework to boost its activity by~830 times.This work presents a mechanistic study of the photocatalytic H2 evolution and energy transfer and highlights the importance of a light-harvesting network for multiple electron injections.展开更多
文摘本文以水溶性柱[6]芳烃(P[6]A)作为主体分子,萘基苯基丙烯腈衍生物(NPA)作为客体分子,两者在水中通过主–客体相互作用形成两亲性复合物,并进一步自组装成纳米颗粒(P[6]A-NPA)。该纳米颗粒可以对荧光染料尼罗红(NiR)进行包载,成功构筑了一种新型水相人工光捕获体系(P[6]A-NPA-NiR)。值得注意的是,当P[6]A-NPA与NiR的摩尔比达到100:1时,该体系的能量转移效率和天线效应分别达到了55%和14.0,为水相超分子人工光捕获领域的研究提供了新思路。A water-soluble pillar[6]arene (P[6]A) was used as host molecule and a naphthalenyl-phenyl-acrylonitrile-based derivative (NPA) was used as guest molecule. The amphiphilic complex of P[6]A-NPA was formed through host-guest interactions in water and further self-assembled into P[6]A-NPA nanoparticles. Moreover, the above nanoparticles can encapsulate the fluorescent dye Nile Red (NiR) and construct a novel aqueous artificial light-harvesting system (P[6]A-NPA-NiR). Notably, when the molar ratio of NPA and NiR reaches 100:1, the energy transfer efficiency and antenna effect of the system reach 55% and 14.0, providing new ideas in the field of aqueous supramolecular artificial light-harvesting systems.
文摘本文设计合成了一种具有聚集诱导效应的苯基吡啶基丙烯腈衍生物(PPAD)作为客体分子,通过与羧酸盐修饰的水溶性柱[5]芳烃(P[5]A)进行主–客体作用,在水中形成了超分子两亲体,并自组装成P[5]A-PPAD超分子纳米颗粒。由于P[5]A-PPAD具有明显的荧光发射能力,可将其作为能量供体,并对能量受体荧光染料4,7-二(2-噻吩基)-2,1,3-苯并噻二唑(DBT)进行包载,成功构筑了一种新型P[5]A-PPAD-DBT超分子人工光捕获体系。通过性能测试发现,P[5]A-PPAD-DBT体系的能量转移效率为52.7%,天线效应为11.6,具有良好的水相人工光捕获能力,为水相人工光捕获体系的构筑与发展提供了新的思路。In this work, a phenylpyridinylacrylonitrile-based derivative (PPAD) with aggregation inducing effect was initially designed and synthesized, which was used as a guest molecule. Through host-guest interaction with a water-soluble pillar[5]arene (P[5]A) modified with carboxylate salts, P[5]A-PPAD supramolecular amphiphilics were formed in water and self-assembled into P[5]A-PPAD supramolecular nanoparticles. Due to the significant fluorescence emission ability of P[5]A-PPAD, P[5]A-PPAD could be used as an energy donor and encapsulate the energy acceptor fluorescent dye 4,7-di(2-thienyl)-2,1,3-benzothiadiazole (DBT) to construct P[5]A-PPAD-DBT supramolecular artificial light harvesting system. After further investigation of light-harvesting performance, the energy transfer efficiency of P[5]A-PPAD-DBT system was 52.7%, and the antenna effect was 11.6, which indicated a good aqueous light-harvesting ability, providing new ideas for the construction and development of supramolecular artificial light harvesting systems.
文摘Molecular catalysts for H2-evolution are of interest for their integration into light-harvesting complexes for photocatalytic water splitting.Here,we report the meso-tetra(4-carboxyphenyl)porphine[(TCPP)Pt^(Ⅱ)]complex as a molecular H2-evolving photocatalyst using chloranilic acid(CA)as a sacrificial electron donor,the choice of which is critical to the stability of the photocatalyst.When triethanolamine was used,[(TCPP)Pt^(Ⅱ)]decomposed to form Pt nanoparticles.Density functional theory calculations together with evidence from electrochemical and spectroscopic analyses suggested that the catalysis was possibly initiated by a proton-coupled electron transfer(PCET)to form[(TCPP)Pt^(Ⅰ)]-N-H,followed by another electron injection and protonation to form a[(TCPP)Pt^(Ⅱ)-hydride]-N-H intermediate that can release H2.As the whole catalytic cycle involves the injection of multiple electrons,a light-harvesting network should be helpful by providing multiple photo-induced electrons.Thus,we integrated this molecular catalyst into a light-harvesting metal-organic framework to boost its activity by~830 times.This work presents a mechanistic study of the photocatalytic H2 evolution and energy transfer and highlights the importance of a light-harvesting network for multiple electron injections.
