The preparation,functionalization,and investigations in host-vip properties of high-level pillararene macrocycles have long been a big challenge because of the lack of efficient synthetic methods.Herein,a novel type...The preparation,functionalization,and investigations in host-vip properties of high-level pillararene macrocycles have long been a big challenge because of the lack of efficient synthetic methods.Herein,a novel type of pillararene derivative,namely desymmetrized pillar[8]arene(DP[8]A),has been successfully synthesized via a facile two-step strategy with high yield.Compared with its pillar[8]arene counterpart,DP[8]A is composed of four alkoxy-substituted benzene units and four bare benzene rings.Single crystal analysis has been performed in order to unveil the molecular conformation and packing mode of DP[8]A,which indicated that DP[8]A possesses a unique chair-like structure and much smaller steric hindrance.Density functional theory(DFT)calculations and electrostatic potential map suggested the inhomogeneous electronic distribution in the DP[8]A cavity.Water-soluble carboxylate-modified DP[8]A,that is,CDP[8]A,was also prepared to investigate the host-vip properties in aqueous solution with methyl viologen(MV),where the binding constant and morphologies of the formed host-vip complexes have been studied.In all,this new version of eight-membered pillararene derivative might potentially serve as a powerful macrocycle candidate for further applications in supramolecular chemistry.展开更多
2,6-Diisopropylaniline reacts with an open-cage fullerene derivative with a 11-membered orifice and forms an open-cage derivative containing one imino group on the rim of the expanded orifice.Further treatment with Le...2,6-Diisopropylaniline reacts with an open-cage fullerene derivative with a 11-membered orifice and forms an open-cage derivative containing one imino group on the rim of the expanded orifice.Further treatment with Lewis acids leads to open-cage fullerenes with an 18-membered orifice.Instead of the direct addition process observed before for less bulky anilines,an electron transfer process takes place in the initial step in the present reaction with bulky 2,6-diisopropylaniline.As a result,the chemo-selectivity is completely different affording the mono imino open-cage derivative selectively.展开更多
π-Conjugated donor-acceptor-donor-acceptor-donor(D-A-D-A-D)type pyrenoviologens(PyV^(2+)),with the 2,7 positions of pyrene serving as connection bridges,were synthesized through SN2 reactions.Specifically,pyrenoviolo...π-Conjugated donor-acceptor-donor-acceptor-donor(D-A-D-A-D)type pyrenoviologens(PyV^(2+)),with the 2,7 positions of pyrene serving as connection bridges,were synthesized through SN2 reactions.Specifically,pyrenoviologen 3c was modified with a methylnaphthalene group,while 3a and 3b were modified with methyl and benzyl groups,respectively,for comparison.These pyrenoviologens exhibit reversible redox properties and strong fluorescence emission.Electrochromic devices(ECDs)were prepared using pyrenoviologens as the active materials.Notably,naphthalene-containing pyrenoviologen 3c,with its DA-D-A-D conjugated structure,possesses more stable free radicals,enabling it to maintain the radical color for a longer duration after power loss.A series of color-changing devices were successfully assembled.Due to the strong fluorescence of pyrenoviologens and the unique electron transfer effect between them and picric acid(PA),a sensor film with good selectivity and high sensitivity for PA in aqueous solution was prepared using pyrenoviologens as the fluorescent probe.Specifically,3c exhibited the highest sensitivity to PA due to its lowest energy gap.The introduction of the D-A-D-A-D structure is a strategic approach to enhancing photoelectric performance and broadening the application of viologens.展开更多
The discovery of novel materials with compelling properties is more accessible with the help of advanced computational algorithms.Recent experimental synthesis of the biphenylene network(C_(6))motivated us to discover...The discovery of novel materials with compelling properties is more accessible with the help of advanced computational algorithms.Recent experimental synthesis of the biphenylene network(C_(6))motivated us to discover new BN-doped biphenylene networks(C_(4)BN,C_(2)B_(2)N_(2),and B_(4)N_(4))and their applications in Li(K)-ion batteries using an evolutionary algorithm and the first-principles calculations.The thermodynamic,thermal,and mechanical stability calculations and decomposition energy suggest the experimental synthesis of predicted biphenylene networks.Adding BN in the biphenylene networks shows a transition from metal to semimetal to semiconductor.The BN biphenylene network shows an HSE06 band gap of 3.06 eV,smaller than h-BN.The C_(4)BN and C_(2)B_(2)N_(2)biphenylene networks offer Li(K)adsorption energy of-0.56 eV(-0.81 eV)and-0.14 eV(-0.28 eV),respectively,with a low diffusion barrier of 178 meV(58 meV)and 251 meV(79 meV),and a large diffusion constant of 8.50×10^(-5)cm^(2)=s(8.78×10^(-3)cm^(2)=s)and 5.33×10^(-6)cm^(2)=s(4.12×10^(-3)cm^(2)=s),respectively.The calculated Li(K)theoretical capacity of C_(4)BN and C_(2)B_(2)N_(2)biphenylene networks is 940.21 mA h g^(-1)(899.01 mA h g^(-1))and 768.08 mA h g^(-1)(808.47 mA h g^(-1)),with a low open circuit voltage of 0.34 V(0.23 V),and 0.17 V(0.13 V),resulting in very high energy density of 2576.18 mW h g^(-1)(2445.31 mW h g^(-1))and 2181.35 mW h g^(-1)(2263.72 mW h g^(-1)),respectively.Only a slight volume change of 1.6%confirms the robustness of BN-doped carbon-based biphenylene networks.Our findings present novel 2D BN-doped biphenylene networks and a pathway toward their applications in metal-ion batteries.展开更多
基金the Natural Science Foundation of Jilin Province(No.20230101052JC)he National Natural Science Foundation of China(Nos.52173200 and 52203138)the Jilin Province Science and Technology Development Plan Project(No.#YDZJ202201ZYTS523)for financial support。
文摘The preparation,functionalization,and investigations in host-vip properties of high-level pillararene macrocycles have long been a big challenge because of the lack of efficient synthetic methods.Herein,a novel type of pillararene derivative,namely desymmetrized pillar[8]arene(DP[8]A),has been successfully synthesized via a facile two-step strategy with high yield.Compared with its pillar[8]arene counterpart,DP[8]A is composed of four alkoxy-substituted benzene units and four bare benzene rings.Single crystal analysis has been performed in order to unveil the molecular conformation and packing mode of DP[8]A,which indicated that DP[8]A possesses a unique chair-like structure and much smaller steric hindrance.Density functional theory(DFT)calculations and electrostatic potential map suggested the inhomogeneous electronic distribution in the DP[8]A cavity.Water-soluble carboxylate-modified DP[8]A,that is,CDP[8]A,was also prepared to investigate the host-vip properties in aqueous solution with methyl viologen(MV),where the binding constant and morphologies of the formed host-vip complexes have been studied.In all,this new version of eight-membered pillararene derivative might potentially serve as a powerful macrocycle candidate for further applications in supramolecular chemistry.
基金supported by Beijing National Laboratory for Molecular Sciences(No.BNLMS-CXXM-201904)National Natural Science Foundation of China(NSFC,Nos.22171009,and 22261039)。
文摘2,6-Diisopropylaniline reacts with an open-cage fullerene derivative with a 11-membered orifice and forms an open-cage derivative containing one imino group on the rim of the expanded orifice.Further treatment with Lewis acids leads to open-cage fullerenes with an 18-membered orifice.Instead of the direct addition process observed before for less bulky anilines,an electron transfer process takes place in the initial step in the present reaction with bulky 2,6-diisopropylaniline.As a result,the chemo-selectivity is completely different affording the mono imino open-cage derivative selectively.
基金supported by the Shaanxi Province Technological Innovation Guidance Special(No.2022QFY08-01)the National Key Research and Development Program of China(No.2021YFB3200702)+5 种基金Natural Science Foundation of China(Nos.22201228,22205172,52203240 and 22175138)China Postdoctoral Science Foundation(Nos.2022M712530,2023T160506,and 2022M712497)Fundamental Research Funds for the Central Universities(No.xzy012022017)Young Talent Fund of Association for Science and Technology in Shaanxi(No.20230624)Shaanxi Province Postdoctoral Science Foundation(No.2023b SHTBZZ04)the Youth Innovation Team of Shaanxi Universities。
文摘π-Conjugated donor-acceptor-donor-acceptor-donor(D-A-D-A-D)type pyrenoviologens(PyV^(2+)),with the 2,7 positions of pyrene serving as connection bridges,were synthesized through SN2 reactions.Specifically,pyrenoviologen 3c was modified with a methylnaphthalene group,while 3a and 3b were modified with methyl and benzyl groups,respectively,for comparison.These pyrenoviologens exhibit reversible redox properties and strong fluorescence emission.Electrochromic devices(ECDs)were prepared using pyrenoviologens as the active materials.Notably,naphthalene-containing pyrenoviologen 3c,with its DA-D-A-D conjugated structure,possesses more stable free radicals,enabling it to maintain the radical color for a longer duration after power loss.A series of color-changing devices were successfully assembled.Due to the strong fluorescence of pyrenoviologens and the unique electron transfer effect between them and picric acid(PA),a sensor film with good selectivity and high sensitivity for PA in aqueous solution was prepared using pyrenoviologens as the fluorescent probe.Specifically,3c exhibited the highest sensitivity to PA due to its lowest energy gap.The introduction of the D-A-D-A-D structure is a strategic approach to enhancing photoelectric performance and broadening the application of viologens.
基金the Khalifa University of Science and Technology through the internal grant RIG-2023-01.
文摘The discovery of novel materials with compelling properties is more accessible with the help of advanced computational algorithms.Recent experimental synthesis of the biphenylene network(C_(6))motivated us to discover new BN-doped biphenylene networks(C_(4)BN,C_(2)B_(2)N_(2),and B_(4)N_(4))and their applications in Li(K)-ion batteries using an evolutionary algorithm and the first-principles calculations.The thermodynamic,thermal,and mechanical stability calculations and decomposition energy suggest the experimental synthesis of predicted biphenylene networks.Adding BN in the biphenylene networks shows a transition from metal to semimetal to semiconductor.The BN biphenylene network shows an HSE06 band gap of 3.06 eV,smaller than h-BN.The C_(4)BN and C_(2)B_(2)N_(2)biphenylene networks offer Li(K)adsorption energy of-0.56 eV(-0.81 eV)and-0.14 eV(-0.28 eV),respectively,with a low diffusion barrier of 178 meV(58 meV)and 251 meV(79 meV),and a large diffusion constant of 8.50×10^(-5)cm^(2)=s(8.78×10^(-3)cm^(2)=s)and 5.33×10^(-6)cm^(2)=s(4.12×10^(-3)cm^(2)=s),respectively.The calculated Li(K)theoretical capacity of C_(4)BN and C_(2)B_(2)N_(2)biphenylene networks is 940.21 mA h g^(-1)(899.01 mA h g^(-1))and 768.08 mA h g^(-1)(808.47 mA h g^(-1)),with a low open circuit voltage of 0.34 V(0.23 V),and 0.17 V(0.13 V),resulting in very high energy density of 2576.18 mW h g^(-1)(2445.31 mW h g^(-1))and 2181.35 mW h g^(-1)(2263.72 mW h g^(-1)),respectively.Only a slight volume change of 1.6%confirms the robustness of BN-doped carbon-based biphenylene networks.Our findings present novel 2D BN-doped biphenylene networks and a pathway toward their applications in metal-ion batteries.
